TY - JOUR A1 - Wang, Qiong A1 - Smith, Joel A. A1 - Skroblin, Dieter A1 - Steele, Julian A. A1 - Wolff, Christian Michael A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Köbler, Hans A1 - Turren-Cruz, Silver-Hamill A1 - Li, Meng A1 - Gollwitzer, Christian A1 - Neher, Dieter A1 - Abate, Antonio T1 - Managing phase purities and crystal orientation for high-performance and photostable cesium lead halide perovskite solar cells JF - Solar RRL N2 - Inorganic perovskites with cesium (Cs+) as the cation have great potential as photovoltaic materials if their phase purity and stability can be addressed. Herein, a series of inorganic perovskites is studied, and it is found that the power conversion efficiency of solar cells with compositions CsPbI1.8Br1.2, CsPbI2.0Br1.0, and CsPbI2.2Br0.8 exhibits a high dependence on the initial annealing step that is found to significantly affect the crystallization and texture behavior of the final perovskite film. At its optimized annealing temperature, CsPbI1.8Br1.2 exhibits a pure orthorhombic phase and only one crystal orientation of the (110) plane. Consequently, this allows for the best efficiency of up to 14.6% and the longest operational lifetime, T-S80, of approximate to 300 h, averaged of over six solar cells, during the maximum power point tracking measurement under continuous light illumination and nitrogen atmosphere. This work provides essential progress on the enhancement of photovoltaic performance and stability of CsPbI3 - xBrx perovskite solar cells. KW - cesium lead halides KW - crystal orientation KW - inorganic perovskites KW - ISOS-L-1I protocol KW - phase purity KW - photostability Y1 - 2020 VL - 4 IS - 9 PB - WILEY-VCH CY - Weinheim ER - TY - GEN A1 - Wang, Qiong A1 - Smith, Joel A. A1 - Skroblin, Dieter A1 - Steele, Julian A. A1 - Wolff, Christian Michael A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Köbler, Hans A1 - Turren-Cruz, Silver-Hamill A1 - Li, Meng A1 - Gollwitzer, Christian A1 - Neher, Dieter A1 - Abate, Antonio T1 - Managing phase purities and crystal orientation for high-performance and photostable cesium lead halide perovskite solar cells T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Inorganic perovskites with cesium (Cs+) as the cation have great potential as photovoltaic materials if their phase purity and stability can be addressed. Herein, a series of inorganic perovskites is studied, and it is found that the power conversion efficiency of solar cells with compositions CsPbI1.8Br1.2, CsPbI2.0Br1.0, and CsPbI2.2Br0.8 exhibits a high dependence on the initial annealing step that is found to significantly affect the crystallization and texture behavior of the final perovskite film. At its optimized annealing temperature, CsPbI1.8Br1.2 exhibits a pure orthorhombic phase and only one crystal orientation of the (110) plane. Consequently, this allows for the best efficiency of up to 14.6% and the longest operational lifetime, T-S80, of approximate to 300 h, averaged of over six solar cells, during the maximum power point tracking measurement under continuous light illumination and nitrogen atmosphere. This work provides essential progress on the enhancement of photovoltaic performance and stability of CsPbI3 - xBrx perovskite solar cells. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1210 KW - cesium lead halides KW - crystal orientation KW - inorganic perovskites KW - ISOS-L-1I protocol KW - phase purity KW - photostability Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-525374 SN - 1866-8372 IS - 9 ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Frischmann, Peter D. A1 - Schulze, Marcus A1 - Bohn, Bernhard J. A1 - Wein, Robin A1 - Livadas, Panajotis A1 - Carlson, Michael T. A1 - Jäckel, Frank A1 - Feldmann, Jochen A1 - Würthner, Frank A1 - Stolarczyk, Jacek K. T1 - All-in-one visible-light-driven water splitting by combining nanoparticulate and molecular co-catalysts on CdS nanorods JF - Nature Energy N2 - Full water splitting into hydrogen and oxygen on semiconductor nanocrystals is a challenging task; overpotentials must be overcome for both half-reactions and different catalytic sites are needed to facilitate them. Additionally, efficient charge separation and prevention of back reactions are necessary. Here, we report simultaneous H-2 and O-2 evolution by CdS nanorods decorated with nanoparticulate reduction and molecular oxidation co-catalysts. The process proceeds entirely without sacrificial agents and relies on the nanorod morphology of CdS to spatially separate the reduction and oxidation sites. Hydrogen is generated on Pt nanoparticles grown at the nanorod tips, while Ru(tpy)(bpy)Cl-2-based oxidation catalysts are anchored through dithiocarbamate bonds onto the sides of the nanorod. O-2 generation from water was verified by O-18 isotope labelling experiments, and time-resolved spectroscopic results confirmed efficient charge separation and ultrafast electron and hole transfer to the reaction sites. The system demonstrates that combining nanoparticulate and molecular catalysts on anisotropic nanocrystals provides an effective pathway for visible-light-driven photocatalytic water splitting. Y1 - 2018 U6 - https://doi.org/10.1038/s41560-018-0229-6 SN - 2058-7546 VL - 3 IS - 10 SP - 862 EP - 869 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Marquez, Jose A. A1 - Nordmann, Joleik A1 - Zhang, Shanshan A1 - Rothhardt, Daniel A1 - Hörmann, Ulrich A1 - Amir, Yohai A1 - Redinger, Alex A1 - Kegelmann, Lukas A1 - Zu, Fengshuo A1 - Albrecht, Steve A1 - Koch, Norbert A1 - Kirchartz, Thomas A1 - Saliba, Michael A1 - Unold, Thomas A1 - Neher, Dieter T1 - The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells JF - Energy & environmental science N2 - Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces. Y1 - 2019 U6 - https://doi.org/10.1039/c9ee02020a SN - 1754-5692 SN - 1754-5706 VL - 12 IS - 9 SP - 2778 EP - 2788 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Saliba, Michael A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Neher, Dieter A1 - Abate, Antonio T1 - Measuring aging stability of perovskite solar cells T2 - Joule Y1 - 2018 U6 - https://doi.org/10.1016/j.joule.2018.05.005 SN - 2542-4351 VL - 2 IS - 6 SP - 1019 EP - 1024 PB - Cell Press CY - Cambridge ER - TY - JOUR A1 - Saliba, Michael A1 - Correa-Baena, Juan-Pablo A1 - Wolff, Christian Michael A1 - Stolterfoht, Martin A1 - Phung, Thi Thuy Nga A1 - Albrecht, Steve A1 - Neher, Dieter A1 - Abate, Antonio T1 - How to Make over 20% Efficient Perovskite Solar Cells in Regular (n-i-p) and Inverted (p-i-n) Architectures JF - Chemistry of materials : a publication of the American Chemical Society N2 - Perovskite solar cells (PSCs) are currently one of the most promising photovoltaic technologies for highly efficient and cost-effective solar energy production. In only a few years, an unprecedented progression of preparation procedures and material compositions delivered lab-scale devices that have now reached record power conversion efficiencies (PCEs) higher than 20%, competing with most established solar cell materials such as silicon, CIGS, and CdTe. However, despite a large number of researchers currently involved in this topic, only a few groups in the world can reproduce >20% efficiencies on a regular n-i-p architecture. In this work, we present detailed protocols for preparing PSCs in regular (n-i-p) and inverted (p-i-n) architectures with >= 20% PCE. We aim to provide a comprehensive, reproducible description of our device fabrication , protocols. We encourage the practice of reporting detailed and transparent protocols that can be more easily reproduced by other laboratories. A better reporting standard may, in turn, accelerate the development of perovskite solar cells and related research fields. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b00136 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 13 SP - 4193 EP - 4201 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Fer, Istem A1 - Tietjen, Britta A1 - Jeltsch, Florian A1 - Wolff, Christian Michael T1 - The influence of El Nino-Southern Oscillation regimes on eastern African vegetation and its future implications under the RCP8.5 warming scenario JF - Biogeosciences N2 - The El Nino-Southern Oscillation (ENSO) is the main driver of the interannual variability in eastern African rainfall, with a significant impact on vegetation and agriculture and dire consequences for food and social security. In this study, we identify and quantify the ENSO contribution to the eastern African rainfall variability to forecast future eastern African vegetation response to rainfall variability related to a predicted intensified ENSO. To differentiate the vegetation variability due to ENSO, we removed the ENSO signal from the climate data using empirical orthogonal teleconnection (EOT) analysis. Then, we simulated the ecosystem carbon and water fluxes under the historical climate without components related to ENSO teleconnections. We found ENSO-driven patterns in vegetation response and confirmed that EOT analysis can successfully produce coupled tropical Pacific sea surface temperature-eastern African rainfall teleconnection from observed datasets. We further simulated eastern African vegetation response under future climate change as it is projected by climate models and under future climate change combined with a predicted increased ENSO intensity. Our EOT analysis highlights that climate simulations are still not good at capturing rainfall variability due to ENSO, and as we show here the future vegetation would be different from what is simulated under these climate model outputs lacking accurate ENSO contribution. We simulated considerable differences in eastern African vegetation growth under the influence of an intensified ENSO regime which will bring further environmental stress to a region with a reduced capacity to adapt effects of global climate change and food security. Y1 - 2017 U6 - https://doi.org/10.5194/bg-14-4355-2017 SN - 1726-4170 SN - 1726-4189 VL - 14 SP - 4355 EP - 4374 PB - Copernicus CY - Göttingen ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Kristen-Jenny, Iris A1 - Schettler, Georg A1 - Plessen, Birgit A1 - Meyer, Hanno A1 - Dulski, Peter A1 - Naumann, Rudolf A1 - Brauer, Achim A1 - Verschuren, Dirk A1 - Haug, Gerald H. T1 - Modern seasonality in Lake Challa (Kenya/Tanzania) and its sedimentary documentation in recent lake sediments JF - Limnology and oceanography N2 - From November 2006 to January 2010, a sediment trap that was cleared monthly was deployed in Lake Challa, a deep stratified freshwater lake on the eastern slope of Mt. Kilimanjaro in southern Kenya. Geochemical data from sediment trap samples were compared with a broad range of limnological and meteorological parameters to characterize the effect of single parameters on productivity and sedimentation processes in the crater basin. During the southern hemisphere summer (November-March), when the water temperature is high and the lake is biologically productive (nondiatom algae), calcite predominated in the sediment trap samples. During the "long rain" season (March-May) a small amount of organic matter and lithogenic material caused by rainfall appeared. This was followed by the cool and windy months of the southern hemisphere winter (June-October) when diatoms were the main component, indicating a diatom bloom initiated by improvement of nutrient availability related to upwelling processes. The sediment trap data support the hypothesis that the light-dark lamination couplets, which are abundant in Lake Challa cores, reflect seasonal delivery to the sediments of diatom-rich particulates during the windy months and diatom-poor material during the wet season. However, interannual and spatial variability in upwelling and productivity patterns, as well as El Nino-Southern Oscillation (ENSO)-related rainfall and drought cycles, exert a strong influence on the magnitude and geochemical composition of particle export to the hypolimnion of Lake Challa. Y1 - 2014 U6 - https://doi.org/10.4319/lo.2014.59.5.1621 SN - 0024-3590 SN - 1939-5590 VL - 59 IS - 5 SP - 1621 EP - 1636 PB - Wiley CY - Waco ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Haug, Gerald H. A1 - Timmermann, Axel A1 - Damste, Jaap S. Sinninghe A1 - Brauer, Achim A1 - Sigman, Daniel M. A1 - Cane, Mark A. A1 - Verschuren, Dirk T1 - Reduced interannual rainfall variability in East Africa during the last Ice Age JF - Science N2 - Interannual rainfall variations in equatorial East Africa are tightly linked to the El Nino Southern Oscillation (ENSO), with more rain and flooding during El Nino and droughts in La Nina years, both having severe impacts on human habitation and food security. Here we report evidence from an annually laminated lake sediment record from southeastern Kenya for interannual to centennial-scale changes in ENSO-related rainfall variability during the last three millennia and for reductions in both the mean rate and the variability of rainfall in East Africa during the Last Glacial period. Climate model simulations support forward extrapolation from these lake sediment data that future warming will intensify the interannual variability of East Africa's rainfall. Y1 - 2011 U6 - https://doi.org/10.1126/science.1203724 SN - 0036-8075 VL - 333 IS - 6043 SP - 743 EP - 747 PB - American Assoc. for the Advancement of Science CY - Washington ER - TY - JOUR A1 - Fohlmeister, Jens Bernd A1 - Plessen, Birgit A1 - Dudashvili, Alexey Sergeevich A1 - Tjallingii, Rik A1 - Wolff, Christian Michael A1 - Gafurov, Abror A1 - Cheng, Hai T1 - Winter precipitation changes during the Medieval Climate Anomaly and the Little Ice Age in arid Central Asia JF - Quaternary science reviews : the international multidisciplinary research and review journal N2 - The strength of the North Atlantic Oscillation (NAO) is considered to be the main driver of climate changes over the European and western Asian continents throughout the last millennium. For example, the predominantly warm Medieval Climate Anomaly (MCA) and the following cold period of the Little Ice Age (LIA) over Europe have been associated with long-lasting phases with a positive and negative NAO index. Its climatic imprint is especially pronounced in European winter seasons. However, little is known about the influence of NAO with respect to its eastern extent over the Eurasian continent. Here we present speleothem records (PC, 8180 and Sr/Ca) from the southern rim of Fergana Basin (Central Asia) revealing annually resolved past climate variations during the last millennium. The age control of the stalagmite relies on radiocarbon dating as large amounts of detrital material inhibit accurate 230Th dating. Present-day calcification of the stalagmite is most effective during spring when the cave atmosphere and elevated water supply by snow melting and high amount of spring precipitation provide optimal conditions. Seasonal precipitation variations cause changes of the stable isotope and Sr/ Ca compositions. The simultaneous changes in these geochemical proxies, however, give also evidence for fractionation processes in the cave. By disentangling both processes, we demonstrate that the amount of winter precipitation during the MCA was generally higher than during the LIA, which is in line with climatic changes linked to the NAO index but opposite to the higher mountain records of Central Asia. Several events of strongly reduced winter precipitation are observed during the LIA in Central Asia. These dry winter events can be related to phases of a strong negative NAO index and all results reveal that winter precipitation over the central Eurasian continent is tightly linked to atmospheric NAO modes by the westerly wind systems. (C) 2017 Elsevier Ltd. All rights reserved. Y1 - 2017 U6 - https://doi.org/10.1016/j.quascirev.2017.10.026 SN - 0277-3791 VL - 178 SP - 24 EP - 36 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Fer, Istem A1 - Tietjen, Britta A1 - Jeltsch, Florian A1 - Wolff, Christian Michael T1 - The influence of El Nino-Southern Oscillation regimes on eastern African vegetation and its future implications under the RCP8.5 warming scenario JF - Biogeosciences N2 - The El Nino-Southern Oscillation (ENSO) is the main driver of the interannual variability in eastern African rainfall, with a significant impact on vegetation and agriculture and dire consequences for food and social security. In this study, we identify and quantify the ENSO contribution to the eastern African rainfall variability to forecast future eastern African vegetation response to rainfall variability related to a predicted intensified ENSO. To differentiate the vegetation variability due to ENSO, we removed the ENSO signal from the climate data using empirical orthogonal teleconnection (EOT) analysis. Then, we simulated the ecosystem carbon and water fluxes under the historical climate without components related to ENSO teleconnections. We found ENSO-driven patterns in vegetation response and confirmed that EOT analysis can successfully produce coupled tropical Pacific sea surface temperature-eastern African rainfall teleconnection from observed datasets. We further simulated eastern African vegetation response under future climate change as it is projected by climate models and under future climate change combined with a predicted increased ENSO intensity. Our EOT analysis highlights that climate simulations are still not good at capturing rainfall variability due to ENSO, and as we show here the future vegetation would be different from what is simulated under these climate model outputs lacking accurate ENSO contribution. We simulated considerable differences in eastern African vegetation growth under the influence of an intensified ENSO regime which will bring further environmental stress to a region with a reduced capacity to adapt effects of global climate change and food security. Y1 - 2017 U6 - https://doi.org/10.5194/bg-14-4355-2017 SN - 1726-4170 SN - 1726-4189 VL - 14 IS - 18 SP - 4355 EP - 4374 PB - Copernicus CY - Katlenburg-Lindau ER - TY - GEN A1 - Fer, Istem A1 - Tietjen, Britta A1 - Jeltsch, Florian A1 - Wolff, Christian Michael T1 - The influence of El Nino-Southern Oscillation regimes on eastern African vegetation and its future implications under the RCP8.5 warming scenario N2 - The El Nino-Southern Oscillation (ENSO) is the main driver of the interannual variability in eastern African rainfall, with a significant impact on vegetation and agriculture and dire consequences for food and social security. In this study, we identify and quantify the ENSO contribution to the eastern African rainfall variability to forecast future eastern African vegetation response to rainfall variability related to a predicted intensified ENSO. To differentiate the vegetation variability due to ENSO, we removed the ENSO signal from the climate data using empirical orthogonal teleconnection (EOT) analysis. Then, we simulated the ecosystem carbon and water fluxes under the historical climate without components related to ENSO teleconnections. We found ENSO-driven patterns in vegetation response and confirmed that EOT analysis can successfully produce coupled tropical Pacific sea surface temperature-eastern African rainfall teleconnection from observed datasets. We further simulated eastern African vegetation response under future climate change as it is projected by climate models and under future climate change combined with a predicted increased ENSO intensity. Our EOT analysis highlights that climate simulations are still not good at capturing rainfall variability due to ENSO, and as we show here the future vegetation would be different from what is simulated under these climate model outputs lacking accurate ENSO contribution. We simulated considerable differences in eastern African vegetation growth under the influence of an intensified ENSO regime which will bring further environmental stress to a region with a reduced capacity to adapt effects of global climate change and food security. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 394 Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-403853 ER - TY - THES A1 - Wolff, Christian Michael T1 - East African monsoon variability since the last glacial T1 - Ostafrikanische Monsunvariabilität seit dem letztem Glazial N2 - 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 Niño Southern Oscillation (ENSO) with more rain and floods during El Niño and severe droughts during La Niña. 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 Niño (La Niña) 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. N2 - Änderungen des Klimas in einer sich erwärmenden Erde haben große Auswirkungen auf den globalen und lokalen Wasserhaushalt und rücken anhand starker Extremereignisse immer häufiger in den Fokus der Öffentlichkeit. Besonders die Regionen der Tropen sind von derartigen Einschnitten stark gefährdet. Der jährliche Niederschlag in Ostafrika ist stark mit der saisonalen Wanderung der ITCZ (Innertropischen Konvergenzzone) sowie mit dem El Niño/Southern Oscillation (ENSO) Phänomen verbunden. Extreme Regenfälle und Überschwemmungen während El Niño Jahren stehen Trockenheit und Dürren in La Niña Jahren gegenüber. Prognosen über zukünftige Veränderungen der ostafrikanischen Niederschläge erfordern ein verbessertes Verständnis der ENSO antreibenden Faktoren. Unglücklicherweise sind die vorhandenen meteorologischen Datenreihen nicht lang genug oder besitzen nicht die benötigte Homogenität. Einen hilfreichen Beitrag können jährlich geschichtete Seesedimente des am Fuße des Kilimandscharo gelegenen Lake Challa leisten. Anhand einer monatlich aufgelösten Sedimentfalle konnte ich nachweisen, dass die rund 25.000 Jahre zurückreichenden Sedimente eine jährliche Struktur besitzen sowie die Dicke dieser jährlichen Schichtung (Warve) stark mit der Dauer und Intensität der saisonal windreichen/trockenen Jahreszeit verbunden ist. Dickere Warven repräsentieren windige/trockene Jahre, wohingegen dünnere Warven für windschwache und feuchte Jahre stehen. Stärkere Winde und kaum Niederschläge treten oft im Zusammenhang mit einem La Niña Ereignis in Ostafrika auf, wohingegen während eines El Niño Ereignisses häufig extreme Niederschläge mit wenig Wind zu beobachten sind. Anhand der Vermessung der Warven kann man verschiedene Klimaparameter rekonstruieren: a) den jährlichen Niederschlag b) jährliche Windgeschwindigkeiten und ihre Intensitäten sowie c) ENSO Variabilitäten. Die in meiner Arbeit gewonnenen klimatischen Informationen zeigen starke Änderungen der ENSO Variabilität innerhalb der letzten 3.000 Jahre mit starken Unterschieden während der Kleinen Eiszeit und während der Mittelalterlichen Warmzeit sowie deutlich trockene und windige Bedingungen mit sehr geringen ENSO Aktivitäten im glazialem Zeitraum (18.500 und 21.000 Jahren). Modellberechnungen unterstützen diese Ergebnisse einer Zunahme von Extremereignissen und feuchteren Bedingungen im Zuge einer Erwärmung des Indischen Ozeans. Mittels geochemischer Analysen der Sedimentfallenproben sowie die daraus resultierende Verknüpfung mit limnologischen und meteorologischen Parametern, konnte ich einen entscheidenden Beitrag zur erfolgreichen Interpretation der existierenden 25.000 Jahre langen μXRF Datensätze leisten. Der Anteil an allochthonem und autochthonem Eintrag kann so genau klassifiziert werden. Das dadurch gewonnene Bild der Klimaentwicklung der letzten 25.000 Jahre deckt sich hervorragend mit anderen Studien und ermöglicht Einblicke in das komplexe Zusammenspiel zwischen Ozean-Atmosphäre und Umwelt auf dem afrikanischen Kontinent. Besonders die für die Ostafrikaforschung extrem hohe Auflösung der Daten wird helfen, die abrupten Klimawechsel und Interaktionen besser verstehen zu können. KW - Lake Challa KW - Sedimentfalle KW - Warve KW - ENSO KW - Monsun KW - Lake Challa KW - sediment trap KW - varve KW - ENSO KW - monsoon Y1 - 2011 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-58079 ER - TY - JOUR A1 - Chen, Zupeng A1 - Savateev, Aleksandr A1 - Pronkin, Sergey A1 - Papaefthimiou, Vasiliki A1 - Wolff, Christian Michael A1 - Willinger, Marc Georg A1 - Willinger, Elena A1 - Neher, Dieter A1 - Antonietti, Markus A1 - Dontsova, Dariya T1 - "The Easier the Better" Preparation of Efficient Photocatalysts-Metastable Poly(heptazine imide) Salts JF - Advanced materials N2 - Cost-efficient, visible-light-driven hydrogen production from water is an attractive potential source of clean, sustainable fuel. Here, it is shown that thermal solid state reactions of traditional carbon nitride precursors (cyanamide, melamine) with NaCl, KCl, or CsCl are a cheap and straightforward way to prepare poly(heptazine imide) alkali metal salts, whose thermodynamic stability decreases upon the increase of the metal atom size. The chemical structure of the prepared salts is confirmed by the results of X-ray photoelectron and infrared spectroscopies, powder X-ray diffraction and electron microscopy studies, and, in the case of sodium poly(heptazine imide), additionally by atomic pair distribution function analysis and 2D powder X-ray diffraction pattern simulations. In contrast, reactions with LiCl yield thermodynamically stable poly(triazine imides). Owing to the metastability and high structural order, the obtained heptazine imide salts are found to be highly active photo-catalysts in Rhodamine B and 4-chlorophenol degradation, and Pt-assisted sacrificial water reduction reactions under visible light irradiation. The measured hydrogen evolution rates are up to four times higher than those provided by a benchmark photocatalyst, mesoporous graphitic carbon nitride. Moreover, the products are able to photocatalytically reduce water with considerable reaction rates, even when glycerol is used as a sacrificial hole scavenger. KW - carbon nitride KW - glycerol oxidation KW - mesocrystals KW - poly(heptazine imide) KW - water reduction reactions Y1 - 2017 U6 - https://doi.org/10.1002/adma.201700555 SN - 0935-9648 SN - 1521-4095 VL - 29 SP - 21800 EP - 21806 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Braunger, Steffen A1 - Mundt, Laura E. A1 - Wolff, Christian Michael A1 - Mews, Mathias A1 - Rehermann, Carolin A1 - Jost, Marko A1 - Tejada, Alvaro A1 - Eisenhauer, David A1 - Becker, Christiane A1 - Andres Guerra, Jorge A1 - Unger, Eva A1 - Korte, Lars A1 - Neher, Dieter A1 - Schubert, Martin C. A1 - Rech, Bernd A1 - Albrecht, Steve T1 - Cs(x)FA(1-x)Pb(l(1-y)Br(y))(3) Perovskite Compositions BT - the Appearance of Wrinkled Morphology and its Impact on Solar Cell Performance JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - We report on the formation of wrinkle-patterned surface morphologies in cesium formamidinium-based Cs(x)FA(1-y)Pb(I1-yBry)(3) perovskite compositions with x = 0-0.3 and y = 0-0.3 under various spin-coating conditions. By varying the Cs and Br contents, the perovskite precursor solution concentration and the spin-coating procedure, the occurrence and characteristics of the wrinkle-shaped morphology can be tailored systematically. Cs(0.17)FA(0.83)Pb(I0.83Br0.17)(3) perovskite layers were analyzed regarding their surface roughness, microscopic structure, local and overall composition, and optoelectronic properties. Application of these films in p-i-n perovskite solar cells (PSCs) with indium-doped tin oxide/NiOx/perovskite/C-60/bathocuproine/Cu architecture resulted in up to 15.3 and 17.0% power conversion efficiency for the flat and wrinkled morphology, respectively. Interestingly, we find slightly red-shifted photoluminescence (PL) peaks for wrinkled areas and we are able to directly correlate surface topography with PL peak mapping. This is attributed to differences in the local grain size, whereas there is no indication for compositional demixing in the films. We show that the perovskite composition, crystallization kinetics, and layer thickness strongly influence the formation of wrinkles which is proposed to be related to the release of compressive strain during perovskite crystallization. Our work helps us to better understand film formation and to further improve the efficiency of PSCs with widely used mixed-perovskite compositions. Y1 - 2018 U6 - https://doi.org/10.1021/acs.jpcc.8b06459 SN - 1932-7447 SN - 1932-7455 VL - 122 IS - 30 SP - 17123 EP - 17135 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kegelmann, Lukas A1 - Tockhorn, Philipp A1 - Wolff, Christian Michael A1 - Márquez, José A. A1 - Caicedo Dávila, Sebastián A1 - Korte, Lars A1 - Unold, Thomas A1 - Loevenich, Wilfried A1 - Neher, Dieter A1 - Rech, Bernd A1 - Albrecht, Steve T1 - Mixtures of Dopant-Free Spiro-OMeTAD and Water-Free PEDOT as a Passivating Hole Contact in Perovskite Solar Cells JF - ACS applied materials & interfaces N2 - Doped spiro-OMeTAD at present is the most commonly used hole transport material (HTM) in n-i-p-type perovskite solar cells, enabling high efficiencies around 22%. However, the required dopants were shown to induce nonradiative recombination of charge carriers and foster degradation of the solar cell. Here, in a novel approach, highly conductive and inexpensive water-free poly(3,4-ethylenedioxythiophene) (PEDOT) is used to replace these dopants. The resulting spiro-OMeTAD/PEDOT (SpiDOT) mixed films achieve higher lateral conductivities than layers of doped spiro-OMeTAD. Furthermore, combined transient and steady-state photoluminescence studies reveal a passivating effect of PEDOT, suppressing nonradiative recombination losses at the perovskite/HTM interface. This enables excellent quasi-Fermi level splitting values of up to 1.24 eV in perovskite/SpiDOT layer stacks and high open-circuit voltages (V-OC) up to 1.19 V in complete solar cells. Increasing the amount of dopant-free spiro-OMeTAD in SpiDOT layers is shown to enhance hole extraction and thereby improves the fill factor in solar cells. As a consequence, stabilized efficiencies up to 18.7% are realized, exceeding cells with doped spiro-OMeTAD as a HTM in this study. Moreover, to the best of our knowledge, these results mark the lowest nonradiative recombination loss in the V-OC (140 mV with respect to the Shockley-Queisser limit) and highest efficiency reported so far for perovskite solar cells using PEDOT as a HTM. KW - perovskite solar cell KW - selective contact KW - spiro-OMeTAD KW - PEDOT KW - recombination KW - passivation KW - quasi-Fermi level splitting Y1 - 2019 U6 - https://doi.org/10.1021/acsami.9b01332 SN - 1944-8244 SN - 1944-8252 VL - 11 IS - 9 SP - 9172 EP - 9181 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zu, Fengshuo A1 - Wolff, Christian Michael A1 - Ralaiarisoa, Maryline A1 - Amsalem, Patrick A1 - Neher, Dieter A1 - Koch, Norbert T1 - Unraveling the Electronic Properties of Lead Halide Perovskites with Surface Photovoltage in Photoemission Studies JF - ACS applied materials & interfaces N2 - The tremendous success of metal-halide perovskites, especially in the field of photovoltaics, has triggered a substantial number of studies in understanding their optoelectronic properties. However, consensus regarding the electronic properties of these perovskites is lacking due to a huge scatter in the reported key parameters, such as work function (Φ) and valence band maximum (VBM) values. Here, we demonstrate that the surface photovoltage (SPV) is a key phenomenon occurring at the perovskite surfaces that feature a non-negligible density of surface states, which is more the rule than an exception for most materials under study. With ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe, we evidence that even minute UV photon fluxes (500 times lower than that used in typical UPS experiments) are sufficient to induce SPV and shift the perovskite Φ and VBM by several 100 meV compared to dark. By combining UV and visible light, we establish flat band conditions (i.e., compensate the surface-state-induced surface band bending) at the surface of four important perovskites, and find that all are p-type in the bulk, despite a pronounced n-type surface character in the dark. The present findings highlight that SPV effects must be considered in all surface studies to fully understand perovskites’ photophysical properties. KW - lead halide perovskite films KW - ultraviolet photoelectron spectroscopy KW - Kelvin probe KW - surface band bending KW - surface photovoltage KW - surface states Y1 - 2019 U6 - https://doi.org/10.1021/acsami.9b05293 SN - 1944-8244 SN - 1944-8252 VL - 11 IS - 24 SP - 21578 EP - 21583 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zu, Fengshuo A1 - Schultz, Thorsten A1 - Wolff, Christian Michael A1 - Shin, Dongguen A1 - Frohloff, Lennart A1 - Neher, Dieter A1 - Amsalem, Patrick A1 - Koch, Norbert T1 - Position-locking of volatile reaction products by atmosphere and capping layers slows down photodecomposition of methylammonium lead triiodide perovskite JF - RSC Advances N2 - The remarkable progress of metal halide perovskites in photovoltaics has led to the power conversion efficiency approaching 26%. However, practical applications of perovskite-based solar cells are challenged by the stability issues, of which the most critical one is photo-induced degradation. Bare CH3NH3PbI3 perovskite films are known to decompose rapidly, with methylammonium and iodine as volatile species and residual solid PbI2 and metallic Pb, under vacuum under white light illumination, on the timescale of minutes. We find, in agreement with previous work, that the degradation is non-uniform and proceeds predominantly from the surface, and that illumination under N-2 and ambient air (relative humidity 20%) does not induce substantial degradation even after several hours. Yet, in all cases the release of iodine from the perovskite surface is directly identified by X-ray photoelectron spectroscopy. This goes in hand with a loss of organic cations and the formation of metallic Pb. When CH3NH3PbI3 films are covered with a few nm thick organic capping layer, either charge selective or non-selective, the rapid photodecomposition process under ultrahigh vacuum is reduced by more than one order of magnitude, and becomes similar in timescale to that under N-2 or air. We conclude that the light-induced decomposition reaction of CH3NH3PbI3, leading to volatile methylammonium and iodine, is largely reversible as long as these products are restrained from leaving the surface. This is readily achieved by ambient atmospheric pressure, as well as a thin organic capping layer even under ultrahigh vacuum. In addition to explaining the impact of gas pressure on the stability of this perovskite, our results indicate that covalently "locking" the position of perovskite components at the surface or an interface should enhance the overall photostability. Y1 - 2020 U6 - https://doi.org/10.1039/d0ra03572f SN - 2046-2069 VL - 10 IS - 30 SP - 17534 EP - 17542 PB - Royal Society of Chemistry CY - Cambridge ER - TY - THES A1 - Wolff, Christian Michael T1 - Identification and reduction of losses in perovskite solar cells N2 - 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. N2 - Auf der Suche nach neuen, kostengünstigen und effizienten Systemen zur photovoltaischen Energiegewinnung, sind Perowskit Solarzellen zu einem der am meistuntersuchtesten Systeme avanciert. Innerhalb einer Dekade konnten unabhängig zertifizierte Umwandlungseffizienzen von >25% in Einzelschicht- und >29% in Mehrschichtzellen basierend auf Siliziumzellen realisiert werden. Die schnelle Entwicklung war in vielerlei Hinsicht glücklich, da beispielsweise die Energielevel typischer Perowskitschichten mit bereits existierenden Kontaktschichtsystemen anderer Photovoltaiksysteme, wie etwa Farbstoffsolarzellen oder Organische Solarzellen, kompatibel sind. Trotz dieses schnellen Erfolges, müssen zur weiteren Effizienzsteigerung grundlegende Wirkprinzipien der Solarzellen verstanden werden. Diese Arbeit beschäftigt sich mit dem umfassenden Verständnis von Rekombinationsprozessen in voll funktionstüchtigen Bauteilen. Zunächst wird der Einfluss unterschiedlicher Energielevel einer Transportschicht, basierend auf Fullerenen untersucht. Dieses kontrovers diskutierte Thema wurde umfassend untersucht und Rekombinationsverluste aufgrund ungünstiger Energielevel reduziert indem - durch die Wahl unterschiedlicher Fulleren-Derivate - der energetische Abstand zwischen Leitungsband des Perowskit und dem niedrigsten unbesetzten Zustand des Fullerenes reduziert wird. Zusätzlich wurde eine ultradünne elektrisch isolierende Zwischenschicht eingebracht, die noch effektiver Rekombinationsverluste unterdrückt, ohne die Fähigkeit zur Ladungsextraktion - und damit Effizienz einzuschränken. Das breite Interesse tausender Forschenden weltweit hat zur schnellen Entwicklung besagter hoher Effizienzen geführt, obgleich verlässliche, leicht nachzuvollziehende Herstellungsprotokolle nicht existierten. Auf Basis der hier entwickelten Protokolle, werden Methoden dargestellt, mit denen verlässlich >20% effiziente Solarzellen produziert werden können. Hierbei wird insbesondere auf sogenannte invertierte (p-i-n) Zellen eingegangen, wobei ein Fokus auf der Beschreibung essentieller Faktoren wie Atmosphärenkontrolle, Temperaturkontrolle, Materialreinheit oder praktischer Erfahrung liegt. Analog zu verlässlichen Herstellungsmethoden bedarf es robuster Techniken um Rekombinationsverluste zu identifizieren und zu lokalisieren. Zu diesem Zweck wird die Messung der absoluten Photolumineszenzeffizienz eingeführt, die erlaubt die Aufspaltung der Quasi-Fermi Level des Perowskiten zu quantifizieren (1.22eV). Ebenso ist es mit dieser Methode möglich Rekombinationsverluste an Grenzflächen zu lokalisieren, die die Leerlaufspannung auf 1.1V limitieren. Zur Vermeidung dieser Verluste werden erneut ultradünne Zwischenschichten an sowohl der p- als auch n- Grenzschicht eingebracht (PFN-P2 und LiF), die Leerlaufspannungen von bis zu 1.17V ermöglichen. Mithilfe eines optimierten Designs und einer Reduzierung der Bandlücke können Bauteile mit 20% Effizienz bei einer Größe von 1cm2 realisiert werden. Nebst hoher Effizienz ist die Stabilität der Bauteile unter einsatzrelevanten Umweltbedingungen ein wichtiger Faktor auf dem Weg zu einer Kommerzialisierung. Dies gilt insbesondere für Hitze, Beleuchtung, elektrische Ladung oder eine Kombination letzterer. Perowskitschichten -- insbesondere diejenigen, die organische Kationen beinhalten -- sind wohlbekannt dafür unter genannten Bedingungen zu degradieren. Das Konzept der ultradünnen Zwischenschichten wird daher um eine Familie fluornierter selbstorganisierender molekularer Monoschichten erweitert X-PFC_n, wobei X ein Halogen I/Br darstellt und n = 7-12 die Länge der fluorinerten Alkylkette angibt), die an der n-Grenzfläche zum Einsatz kommen. Diese Zwischenschicht reduziert Rekombinationsverluste resultierend in 21.3% effizienten Bauteilen und ermöglicht zusätzlich eine drastische erhöhte Stabilität. Bauteile mit dem Molekül IPFC10 sind über 3000h stabil unter Lagerungsbedingungen im Dunkeln und überstehen 250h unter voller Last bei 85°C ohne nennenswerte Verluste. Weitere Fortschritte in der Steigerung der Effizienz sind nur zu erwarten, wenn eine vollständige Beschreibung der Wirkprinzipien und Schwachstellen vorliegt. Eine Vielzahl experimenteller Studien haben bisher jedoch ein lückenhaftes Bild gemalt. Häufig sind physikalische Beschränkungen, etwa die hohe Kapazität aufgrund der sehr dünnen Schichten dafür verantwortlich, dass Rekombinationsdynamiken durch kapazitive Entladungsprozesse verdeckt werden. Um diese Probleme zu umgehen, werden hocheffiziente Solarzellen mit einer Kombination mehrerer optischer und optoelektronischer Messmethoden untersucht. Dies ermöglicht die Rekombinationsdynamik mit einer Superposition aus Rekombination erster, zweiter und dritter Ordnung der Ladungsträgerdichte vollumfänglich zu beschreiben. Drift-Diffusions Simulationen unterstützen die experimentellen Ergebnisse, selbst unter Einbeziehung mobiler Ionen. Weiterhin wird in einem Übersichtsartikel ein Ausblick auf den gegenwärtigen Stand des Wissens im Bezug auf Rekombinationsverluste in besagten Solarzellen gegeben. Unterschiedliche Messmethoden werden vorgestellt und erfolgreiche Methoden zur Minderung genannter Verluste diskutiert. Insgesamt stellt diese Arbeit einen Fortschritt im Verständnis und der Verminderung unterschiedlicher Verlustprozesse dar. Mithilfe unterschiedlicher verlässlicher optoelektronischer Messmethoden, wird gezeigt, dass der Ursprung von Rekombinations- und Stabilitätsverlusten häufig an den Grenzflächen liegt. Mithilfe gezielt eingesetzter ultradünner Zwischenschichten werden diese Verluste reduziert und die Stabilität erhöht. T2 - Identifizierung und Reduzierung von Verlusten in Perowskit Solarzellen KW - perovskite solar cells KW - interfacial recombination KW - nonradiative losses KW - Perowskit Solarzellen KW - Grenzflächenrekombination KW - nichtstrahlende Verluste Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-479301 ER - TY - JOUR A1 - Kegelmann, Lukas A1 - Wolff, Christian Michael A1 - Awino, Celline A1 - Lang, Felix A1 - Unger, Eva L. A1 - Korte, Lars A1 - Dittrich, Thomas A1 - Neher, Dieter A1 - Rech, Bernd A1 - Albrecht, Steve T1 - It Takes Two to Tango-Double-Layer Selective Contacts in Perovskite Solar Cells for Improved Device Performance and Reduced Hysteresis JF - ACS applied materials & interfaces N2 - Solar cells made from inorganic organic perovskites have gradually approached market requirements as their efficiency and stability have improved tremendously in recent years. Planar low-temperature processed perovskite solar cells are advantageous for possible large-scale production but are more prone to exhibiting photocurrent hysteresis, especially in the regular n-i-p structure. Here, a systematic characterization of different electron selective contacts with a variety of chemical and electrical properties in planar n-i-p devices processed below 180 degrees C is presented. The inorganic metal oxides TiO2 and SnO2, the organic fullerene derivatives C-60, PCBM, and ICMA, as well as double-layers with a metal oxide/PCBM structure are used as electron transport materials (ETMs). Perovskite layers deposited atop, the different ETMs with the herein applied fabrication method show a similar morphology according to scanning electron microscopy. Further, surface photovoltage spectroscopy measurements indicate comparable perovskite absorber qualities on all ETMs, except TiO2, which shows a more prominent influence of defect states. Transient photoluminescence studies together with current voltage scans over a broad range of scan speeds reveal faster charge extraction, less pronounced hysteresis effects, and higher efficiencies for devices with fullerene compared to those with metal oxide ETMs. Beyond this, only double-layer ETM structures substantially diminish hysteresis effects for all performed scan speeds and strongly enhance the power conversion efficiency up to a champion stabilized value of 18.0%. The results indicate reduced recombination losses for a double-layer TiO2/PCBM contact design: First, a reduction of shunt paths through the fullerene to the ITO layer. Second, an improved hole blocking by the wide band gap metal oxide. Third, decreased transport losses due to an energetically more favorable contact, as implied by photoelectron spectroscopy measurements. The herein demonstrated improvements of multilayer selective contacts may serve as a general design guideline for perovskite solar cells. KW - perovskite solar cell KW - electron contact KW - double-layer KW - regular planar architecture KW - hysteresis KW - fullerene KW - metal oxide Y1 - 2017 U6 - https://doi.org/10.1021/acsami.7b00900 SN - 1944-8244 VL - 9 SP - 17246 EP - 17256 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wang, Qiong A1 - Mosconi, Edoardo A1 - Wolff, Christian Michael A1 - Li, Junming A1 - Neher, Dieter A1 - De Angelis, Filippo A1 - Suranna, Gian Paolo A1 - Grisorio, Roberto A1 - Abate, Antonio T1 - Rationalizing the molecular design of hole-selective contacts to improve charge extraction in Perovskite solar cells JF - dvanced energy materials N2 - Two new hole selective materials (HSMs) based on dangling methylsulfanyl groups connected to the C-9 position of the fluorene core are synthesized and applied in perovskite solar cells. Being structurally similar to a half of Spiro-OMeTAD molecule, these HSMs (referred as FS and DFS) share similar redox potentials but are endowed with slightly higher hole mobility, due to the planarity and large extension of their structure. Competitive power conversion efficiency (up to 18.6%) is achieved by using the new HSMs in suitable perovskite solar cells. Time-resolved photoluminescence decay measurements and electrochemical impedance spectroscopy show more efficient charge extraction at the HSM/perovskite interface with respect to Spiro-OMeTAD, which is reflected in higher photocurrents exhibited by DFS/FS-integrated perovskite solar cells. Density functional theory simulations reveal that the interactions of methylammonium with methylsulfanyl groups in DFS/FS strengthen their electrostatic attraction with the perovskite surface, providing an additional path for hole extraction compared to the sole presence of methoxy groups in Spiro-OMeTAD. Importantly, the low-cost synthesis of FS makes it significantly attractive for the future commercialization of perovskite solar cells. KW - hole extraction KW - hole selective materials KW - perovskite solar cells KW - sulfur KW - triple-cation perovskite Y1 - 2019 U6 - https://doi.org/10.1002/aenm.201900990 SN - 1614-6832 SN - 1614-6840 VL - 9 IS - 28 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Jošt, Marko A1 - Albrecht, Steve A1 - Kegelmann, Lukas A1 - Wolff, Christian Michael A1 - Lang, Felix A1 - Lipovšek, Benjamin A1 - Krč, Janez A1 - Korte, Lars A1 - Neher, Dieter A1 - Rech, Bernd A1 - Topič, Marko T1 - Efficient light management by textured nanoimprinted layers for perovskite solar cells JF - ACS photonics N2 - Inorganic-organic perovskites like methylammonium-lead-iodide have proven to be an effective class of 17 materials for fabricating efficient solar cells. To improve their performance, light management techniques using textured surfaces, similar to those used in established solar cell technologies, should be considered. Here, we apply a light management foil created by UV nanoimprint lithography on the glass side of an inverted (p-i-n) perovskite solar cell with 16.3% efficiency. The obtained 1 mA cm(-2) increase in the short-circuit current density translates to a relative improvement in cell performance of 5%, which results in a power conversion efficiency of 17.1%. Optical 3D simulations based on experimentally obtained parameters were used to support the experimental findings. A good match between the simulated and experimental data was obtained, validating the model. Optical simulations reveal that the main improvement in device performance is due to a reduction in total reflection and that relative improvement in the short-circuit current density of up to 10% is possible for large-area devices. Therefore, our results present the potential of light management foils for improving the device performance of perovskite solar cells and pave the way for further use of optical simulations in the field of perovskite solar cells. KW - perovskite solar cells KW - antireflection KW - light management KW - UV nanoimprint lithography KW - optical simulations Y1 - 2017 U6 - https://doi.org/10.1021/acsphotonics.7b00138 SN - 2330-4022 VL - 4 SP - 1232 EP - 1239 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zu, Fengshuo A1 - Amsalem, Patrick A1 - Egger, David A. A1 - Wang, Rongbin A1 - Wolff, Christian Michael A1 - Fang, Honghua A1 - Loi, Maria Antonietta A1 - Neher, Dieter A1 - Kronik, Leeor A1 - Duhm, Steffen A1 - Koch, Norbert T1 - Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements JF - The journal of physical chemistry letters N2 - Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpclett.8b03728 SN - 1948-7185 VL - 10 IS - 3 SP - 601 EP - 609 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Paulke, Andreas A1 - Stranks, Samuel D. A1 - Kniepert, Juliane A1 - Kurpiers, Jona A1 - Wolff, Christian Michael A1 - Schön, Natalie A1 - Snaith, Henry J. A1 - Brenner, Thomas J. K. A1 - Neher, Dieter T1 - Charge carrier recombination dynamics in perovskite and polymer solar cells JF - Applied physics letters N2 - Time-delayed collection field experiments are applied to planar organometal halide perovskite (CH3NH3PbI3) based solar cells to investigate charge carrier recombination in a fully working solar cell at the nanosecond to microsecond time scale. Recombination of mobile (extractable) charges is shown to follow second-order recombination dynamics for all fluences and time scales tested. Most importantly, the bimolecular recombination coefficient is found to be time-dependent, with an initial value of ca. 10(-9) cm(3)/s and a progressive reduction within the first tens of nanoseconds. Comparison to the prototypical organic bulk heterojunction device PTB7:PC71BM yields important differences with regard to the mechanism and time scale of free carrier recombination. (C) 2016 AIP Publishing LLC. Y1 - 2016 U6 - https://doi.org/10.1063/1.4944044 SN - 0003-6951 SN - 1077-3118 VL - 108 SP - 252 EP - 262 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Love, John A. A1 - Feuerstein, Markus A1 - Wolff, Christian Michael A1 - Facchetti, Antonio A1 - Neher, Dieter T1 - Lead Halide Perovskites as Charge Generation Layers for Electron Mobility Measurement in Organic Semiconductors JF - ACS applied materials & interfaces N2 - Hybrid lead halide perovskites are introduced as charge generation layers (CGLs) for the accurate determination of electron mobilities in thin organic semiconductors. Such hybrid perovskites have become a widely studied photovoltaic material in their own right, for their high efficiencies, ease of processing from solution, strong absorption, and efficient photogeneration of charge. Time-of-flight (ToF) measurements on bilayer samples consisting of the perovskite CGL and an organic semiconductor layer of different thickness are shown to be determined by the carrier motion through the organic material, consistent with the much higher charge carrier mobility in the perovskite. Together with the efficient photon-to-electron conversion in the perovskite, this high mobility imbalance enables electron-only mobility measurement on relatively thin application-relevant organic films, which would not be possible with traditional ToF measurements. This architecture enables electron-selective mobility measurements in single components as well as bulk-heterojunction films as demonstrated in the prototypical polymer/fullerene blends. To further demonstrate the potential of this approach, electron mobilities were measured as a function of electric field and temperature in an only 127 nm thick layer of a prototypical electron-transporting perylene diimide-based polymer, and found to be consistent with an exponential trap distribution of ca. 60 meV. Our study furthermore highlights the importance of high mobility charge transporting layers when designing perovskite solar cells. KW - mobility KW - bulk heterojunction KW - time of flight KW - lead halide perovskites KW - charge generation layers Y1 - 2017 U6 - https://doi.org/10.1021/acsami.7b10361 SN - 1944-8244 VL - 9 SP - 42011 EP - 42019 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Zu, Fengshuo A1 - Paulke, Andreas A1 - Perdigón-Toro, Lorena A1 - Koch, Norbert A1 - Neher, Dieter T1 - Reduced Interface-Mediated Recombination for High Open-Circuit Voltages in CH3NH3PbI3 Solar Cells JF - Advanced materials N2 - Perovskite solar cells with all-organic transport layers exhibit efficiencies rivaling their counterparts that employ inorganic transport layers, while avoiding high-temperature processing. Herein, it is investigated how the choice of the fullerene derivative employed in the electron-transporting layer of inverted perovskite cells affects the open-circuit voltage (V-OC). It is shown that nonradiative recombination mediated by the electron-transporting layer is the limiting factor for the V-OC in the cells. By inserting an ultrathin layer of an insulating polymer between the active CH3NH3PbI3 perovskite and the fullerene, an external radiative efficiency of up to 0.3%, a V-OC as high as 1.16 V, and a power conversion efficiency of 19.4% are realized. The results show that the reduction of nonradiative recombination due to charge-blocking at the perovskite/organic interface is more important than proper level alignment in the search for ideal selective contacts toward high V-OC and efficiency. KW - electron-transport layers KW - nonradiative recombination KW - open-circuit voltage KW - perovskite solar cells Y1 - 2017 U6 - https://doi.org/10.1002/adma.201700159 SN - 0935-9648 SN - 1521-4095 VL - 29 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Unold, Thomas A1 - Rech, Bernd A1 - Albrecht, Steve A1 - Neher, Dieter T1 - On the relation between the open‐circuit voltage and quasi‐Fermi level splitting in efficient perovskite solar cells T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - Today's perovskite solar cells (PSCs) are limited mainly by their open‐circuit voltage (VOC) due to nonradiative recombination. Therefore, a comprehensive understanding of the relevant recombination pathways is needed. Here, intensity‐dependent measurements of the quasi‐Fermi level splitting (QFLS) and of the VOC on the very same devices, including pin‐type PSCs with efficiencies above 20%, are performed. It is found that the QFLS in the perovskite lies significantly below its radiative limit for all intensities but also that the VOC is generally lower than the QFLS, violating one main assumption of the Shockley‐Queisser theory. This has far‐reaching implications for the applicability of some well‐established techniques, which use the VOC as a measure of the carrier densities in the absorber. By performing drift‐diffusion simulations, the intensity dependence of the QFLS, the QFLS‐VOC offset and the ideality factor are consistently explained by trap‐assisted recombination and energetic misalignment at the interfaces. Additionally, it is found that the saturation of the VOC at high intensities is caused by insufficient contact selectivity while heating effects are of minor importance. It is concluded that the analysis of the VOC does not provide reliable conclusions of the recombination pathways and that the knowledge of the QFLS‐VOC relation is of great importance. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 774 KW - electro‐optical materials KW - perovskite solar cells KW - photovoltaic devices KW - thin films Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437595 SN - 1866-8372 IS - 774 ER - TY - JOUR A1 - Zhang, Shanshan A1 - Hosseini, Seyed Mehrdad A1 - Gunder, Rene A1 - Petsiuk, Andrei A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Shoaee, Safa A1 - Meredith, Paul A1 - Schorr, Susan A1 - Unold, Thomas A1 - Burn, Paul L. A1 - Neher, Dieter A1 - Stolterfoht, Martin T1 - The Role of Bulk and Interface Recombination in High-Efficiency Low-Dimensional Perovskite Solar Cells JF - Advanced materials N2 - 2D Ruddlesden-Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite-based cells. Herein, 2D (CH3(CH2)(3)NH3)(2)(CH3NH3)(n-1)PbnI3n+1 perovskite cells with different numbers of [PbI6](4-) sheets (n = 2-4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open-circuit voltage (V-OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C-60 interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi-Fermi level splitting matches the device V-OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements. KW - 2D perovskites KW - interface recombination KW - perovskite solar cells KW - photoluminescence KW - V-OC loss Y1 - 2019 U6 - https://doi.org/10.1002/adma.201901090 SN - 0935-9648 SN - 1521-4095 VL - 31 IS - 30 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Caprioglio, Pietro A1 - Zu, Fengshuo A1 - Wolff, Christian Michael A1 - Prieto, Jose A. Marquez A1 - Stolterfoht, Martin A1 - Becker, Pascal A1 - Koch, Norbert A1 - Unold, Thomas A1 - Rech, Bernd A1 - Albrecht, Steve A1 - Neher, Dieter T1 - High open circuit voltages in pin-type perovskite solar cells through strontium addition JF - Sustainable Energy & Fuels N2 - The incorporation of even small amounts of strontium (Sr) into lead-base hybrid quadruple cation perovskite solar cells results in a systematic increase of the open circuit voltage (V-oc) in pin-type perovskite solar cells. We demonstrate via absolute and transient photoluminescence (PL) experiments how the incorporation of Sr significantly reduces the non-radiative recombination losses in the neat perovskite layer. We show that Sr segregates at the perovskite surface, where it induces important changes of morphology and energetics. Notably, the Sr-enriched surface exhibits a wider band gap and a more n-type character, accompanied with significantly stronger surface band bending. As a result, we observe a significant increase of the quasi-Fermi level splitting in the neat perovskite by reduced surface recombination and more importantly, a strong reduction of losses attributed to non-radiative recombination at the interface to the C-60 electron-transporting layer. The resulting solar cells exhibited a V-oc of 1.18 V, which could be further improved to nearly 1.23 V through addition of a thin polymer interlayer, reducing the non-radiative voltage loss to only 110 meV. Our work shows that simply adding a small amount of Sr to the precursor solutions induces a beneficial surface modification in the perovskite, without requiring any post treatment, resulting in high efficiency solar cells with power conversion efficiency (PCE) up to 20.3%. Our results demonstrate very high V-oc values and efficiencies in Sr-containing quadruple cation perovskite pin-type solar cells and highlight the imperative importance of addressing and minimizing the recombination losses at the interface between perovskite and charge transporting layer. Y1 - 2019 U6 - https://doi.org/10.1039/c8se00509e SN - 2398-4902 VL - 3 IS - 2 SP - 550 EP - 563 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Unold, Thomas A1 - Rech, Bernd A1 - Albrecht, Steve A1 - Neher, Dieter T1 - On the relation between the open-circuit voltage and quasi-fermi level splitting in efficient perovskite solar cells JF - advanced energy materials N2 - Today's perovskite solar cells (PSCs) are limited mainly by their open‐circuit voltage (VOC) due to nonradiative recombination. Therefore, a comprehensive understanding of the relevant recombination pathways is needed. Here, intensity‐dependent measurements of the quasi‐Fermi level splitting (QFLS) and of the VOC on the very same devices, including pin‐type PSCs with efficiencies above 20%, are performed. It is found that the QFLS in the perovskite lies significantly below its radiative limit for all intensities but also that the VOC is generally lower than the QFLS, violating one main assumption of the Shockley‐Queisser theory. This has far‐reaching implications for the applicability of some well‐established techniques, which use the VOC as a measure of the carrier densities in the absorber. By performing drift‐diffusion simulations, the intensity dependence of the QFLS, the QFLS‐VOC offset and the ideality factor are consistently explained by trap‐assisted recombination and energetic misalignment at the interfaces. Additionally, it is found that the saturation of the VOC at high intensities is caused by insufficient contact selectivity while heating effects are of minor importance. It is concluded that the analysis of the VOC does not provide reliable conclusions of the recombination pathways and that the knowledge of the QFLS‐VOC relation is of great importance. KW - electro-optical materials KW - perovskite solar cells KW - photovoltaic devices KW - thin films Y1 - 2019 U6 - https://doi.org/10.1002/aenm.201901631 SN - 1614-6832 SN - 1614-6840 VL - 9 IS - 33 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Le Corre, Vincent M. A1 - Stolterfoht, Martin A1 - Perdigón-Toro, Lorena A1 - Feuerstein, Markus A1 - Wolff, Christian Michael A1 - Gil-Escrig, Lidon A1 - Bolink, Henk J. A1 - Neher, Dieter A1 - Koster, L. Jan Anton T1 - Charge Transport Layers Limiting the Efficiency of Perovskite Solar Cells: How To Optimize Conductivity, Doping, and Thickness JF - ACS Applied Energy Materials N2 - Perovskite solar cells (PSCs) are one of the main research topics of the photovoltaic community; with efficiencies now reaching up to 24%, PSCs are on the way to catching up with classical inorganic solar cells. However, PSCs have not yet reached their full potential. In fact, their efficiency is still limited by nonradiative recombination, mainly via trap-states and by losses due to the poor transport properties of the commonly used transport layers (TLs). Indeed, state-of-the-art TLs (especially if organic) suffer from rather low mobilities, typically within 10(-5) and 10(-2) cm(-2) V-1 s(-1), when compared to the high mobilities, 1-10 cm(-2) V-1 s(-1), measured for perovskites. This work presents a comprehensive analysis of the effect of the mobility, thickness, and doping density of the transport layers based on combined experimental and modeling results of two sets of devices made of a solution-processed high-performing triple-cation (PCE approximate to 20%). The results are also cross-checked on vacuum-processed MAPbI(3) devices. From this analysis, general guidelines on how to optimize a TL are introduced and especially a new and simple formula to easily calculate the amount of doping necessary to counterbalance the low mobility of the TLs. KW - perovskite solar cells KW - transport layers KW - conductivity KW - doping KW - charge transport Y1 - 2019 U6 - https://doi.org/10.1021/acsaem.9b00856 SN - 2574-0962 VL - 2 IS - 9 SP - 6280 EP - 6287 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Würfel, Uli A1 - Perdigón-Toro, Lorena A1 - Kurpiers, Jona A1 - Wolff, Christian Michael A1 - Caprioglio, Pietro A1 - Rech, Jeromy James A1 - Zhu, Jingshuai A1 - Zhan, Xiaowei A1 - You, Wei A1 - Shoaee, Safa A1 - Neher, Dieter A1 - Stolterfoht, Martin T1 - Recombination between Photogenerated and Electrode-Induced Charges Dominates the Fill Factor Losses in Optimized Organic Solar Cells JF - The journal of physical chemistry letters N2 - Charge extraction in organic solar cells (OSCs) is commonly believed to be limited by bimolecular recombination of photogenerated charges. However, the fill factor of OSCs is usually almost entirely governed by recombination processes that scale with the first order of the light intensity. This linear loss was often interpreted to be a consequence of geminate or trap-assisted recombination. Numerical simulations show that this linear dependence is a direct consequence of the large amount of excess dark charge near the contact. The first-order losses increase with decreasing mobility of minority carriers, and we discuss the impact of several material and device parameters on this loss mechanism. This work highlights that OSCs are especially vulnerable to injected charges as a result of their poor charge transport properties. This implies that dark charges need to be better accounted for when interpreting electro-optical measurements and charge collection based on simple figures of merit. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpclett.9b01175 SN - 1948-7185 VL - 10 IS - 12 SP - 3473 EP - 3480 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Perdigón-Toro, Lorena A1 - Zhang, Huotian A1 - Markina, Anastaa si A1 - Yuan, Jun A1 - Hosseini, Seyed Mehrdad A1 - Wolff, Christian Michael A1 - Zuo, Guangzheng A1 - Stolterfoht, Martin A1 - Zou, Yingping A1 - Gao, Feng A1 - Andrienko, Denis A1 - Shoaee, Safa A1 - Neher, Dieter T1 - Barrierless free charge generation in the high-performance PM6:Y6 bulk heterojunction non-fullerene solar cell JF - Advanced materials N2 - Organic solar cells are currently experiencing a second golden age thanks to the development of novel non-fullerene acceptors (NFAs). Surprisingly, some of these blends exhibit high efficiencies despite a low energy offset at the heterojunction. Herein, free charge generation in the high-performance blend of the donor polymer PM6 with the NFA Y6 is thoroughly investigated as a function of internal field, temperature and excitation energy. Results show that photocurrent generation is essentially barrierless with near-unity efficiency, regardless of excitation energy. Efficient charge separation is maintained over a wide temperature range, down to 100 K, despite the small driving force for charge generation. Studies on a blend with a low concentration of the NFA, measurements of the energetic disorder, and theoretical modeling suggest that CT state dissociation is assisted by the electrostatic interfacial field which for Y6 is large enough to compensate the Coulomb dissociation barrier. KW - driving force KW - non-fullerene acceptors KW - organic solar cells KW - photocurrent generation Y1 - 2020 U6 - https://doi.org/10.1002/adma.201906763 SN - 0935-9648 SN - 1521-4095 VL - 32 IS - 9 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Wolff, Christian Michael A1 - Canil, Laura A1 - Rehermann, Carolin A1 - Nguyen, Ngoc Linh A1 - Zu, Fengshuo A1 - Ralaiarisoa, Maryline A1 - Caprioglio, Pietro A1 - Fiedler, Lukas A1 - Stolterfoht, Martin A1 - Kogikoski, Junior, Sergio A1 - Bald, Ilko A1 - Koch, Norbert A1 - Unger, Eva L. A1 - Dittrich, Thomas A1 - Abate, Antonio A1 - Neher, Dieter T1 - Correction to 'Perfluorinated self-assembled monolayers enhance the stability and efficiency of inverted perovskite solar cells' (2020, 14 (2), 1445−1456) T2 - ACS nano Y1 - 2020 U6 - https://doi.org/10.1021/acsnano.0c08081 SN - 1936-0851 SN - 1936-086X VL - 14 IS - 11 SP - 16156 EP - 16156 PB - American Chemical Society CY - Washington, DC ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Amir, Yohai A1 - Paulke, Andreas A1 - Perdigón-Toro, Lorena A1 - Caprioglio, Pietro A1 - Neher, Dieter T1 - Approaching the fill factor Shockley-Queisser limit in stable, dopant-free triple cation perovskite solar cells JF - Energy & Environmental Science N2 - Perovskite solar cells now compete with their inorganic counterparts in terms of power conversion efficiency, not least because of their small open-circuit voltage (V-OC) losses. A key to surpass traditional thin-film solar cells is the fill factor (FF). Therefore, more insights into the physical mechanisms that define the bias dependence of the photocurrent are urgently required. In this work, we studied charge extraction and recombination in efficient triple cation perovskite solar cells with undoped organic electron/hole transport layers (ETL/HTL). Using integral time of flight we identify the transit time through the HTL as the key figure of merit for maximizing the fill factor (FF) and efficiency. Complementarily, intensity dependent photocurrent and V-OC measurements elucidate the role of the HTL on the bias dependence of non-radiative and transport-related loss channels. We show that charge transport losses can be completely avoided under certain conditions, yielding devices with FFs of up to 84%. Optimized cells exhibit power conversion efficiencies of above 20% for 6 mm(2) sized pixels and 18.9% for a device area of 1 cm(2). These are record efficiencies for hybrid perovskite devices with dopant-free transport layers, highlighting the potential of this device technology to avoid charge-transport limitations and to approach the Shockley-Queisser limit. Y1 - 2017 U6 - https://doi.org/10.1039/c7ee00899f SN - 1754-5692 SN - 1754-5706 VL - 10 SP - 1530 EP - 1539 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Wolff, Christian Michael A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Neher, Dieter T1 - Nonradiative recombination in perovskite solar cells BT - the role of interfaces T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their VOC to values well below the Shockley–Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi‐Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the VOC of operational devices. These measurements prove that in state‐of‐the‐art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump‐probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome—paving the way to the thermodynamic efficiency limit. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 772 KW - interfacial recombination KW - open‐circuit voltage KW - perovskite solar cells KW - photoluminescence Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437626 SN - 1866-8372 IS - 772 ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Neher, Dieter T1 - Nonradiative Recombination in Perovskite Solar Cells BT - the Role of Interfaces JF - Advanced materials N2 - Perovskite solar cells combine high carrier mobilities with long carrier lifetimes and high radiative efficiencies. Despite this, full devices suffer from significant nonradiative recombination losses, limiting their V-OC to values well below the Shockley-Queisser limit. Here, recent advances in understanding nonradiative recombination in perovskite solar cells from picoseconds to steady state are presented, with an emphasis on the interfaces between the perovskite absorber and the charge transport layers. Quantification of the quasi-Fermi level splitting in perovskite films with and without attached transport layers allows to identify the origin of nonradiative recombination, and to explain the V-OC of operational devices. These measurements prove that in state-of-the-art solar cells, nonradiative recombination at the interfaces between the perovskite and the transport layers is more important than processes in the bulk or at grain boundaries. Optical pump-probe techniques give complementary access to the interfacial recombination pathways and provide quantitative information on transfer rates and recombination velocities. Promising optimization strategies are also highlighted, in particular in view of the role of energy level alignment and the importance of surface passivation. Recent record perovskite solar cells with low nonradiative losses are presented where interfacial recombination is effectively overcome-paving the way to the thermodynamic efficiency limit. KW - interfacial recombination KW - open-circuit voltage KW - perovskite solar cells KW - photoluminescence Y1 - 2019 U6 - https://doi.org/10.1002/adma.201902762 SN - 0935-9648 SN - 1521-4095 VL - 31 IS - 52 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Marquez, Jose A. A1 - Zhang, Shanshan A1 - Hages, Charles J. A1 - Rothhardt, Daniel A1 - Albrecht, Steve A1 - Burn, Paul L. A1 - Meredith, Paul A1 - Unold, Thomas A1 - Neher, Dieter T1 - Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells JF - Nature Energy N2 - The performance of perovskite solar cells is predominantly limited by non-radiative recombination, either through trap-assisted recombination in the absorber layer or via minority carrier recombination at the perovskite/transport layer interfaces. Here, we use transient and absolute photoluminescence imaging to visualize all non-radiative recombination pathways in planar pintype perovskite solar cells with undoped organic charge transport layers. We find significant quasi-Fermi-level splitting losses (135 meV) in the perovskite bulk, whereas interfacial recombination results in an additional free energy loss of 80 meV at each individual interface, which limits the open-circuit voltage (V-oc) of the complete cell to similar to 1.12 V. Inserting ultrathin interlayers between the perovskite and transport layers leads to a substantial reduction of these interfacial losses at both the p and n contacts. Using this knowledge and approach, we demonstrate reproducible dopant-free 1 cm(2) perovskite solar cells surpassing 20% efficiency (19.83% certified) with stabilized power output, a high V-oc (1.17 V) and record fill factor (>81%). KW - Energy science and technology KW - Solar cells Y1 - 2018 U6 - https://doi.org/10.1038/s41560-018-0219-8 SN - 2058-7546 VL - 3 IS - 10 SP - 847 EP - 854 PB - Nature Publ. Group CY - London ER - TY - GEN A1 - Stolterfoht, Martin A1 - Grischek, Max A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Gutierrez-Partida, Emilio A1 - Peña-Camargo, Francisco A1 - Rothhardt, Daniel A1 - Zhang, Shanshan A1 - Raoufi, Meysam A1 - Wolansky, Jakob A1 - Abdi-Jalebi, Mojtaba A1 - Stranks, Samuel D. A1 - Albrecht, Steve A1 - Kirchartz, Thomas A1 - Neher, Dieter T1 - How to quantify the efficiency potential of neat perovskite films BT - Perovskite semiconductors with an implied efficiency exceeding 28% T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are not limited by Auger recombination under 1-sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non-radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open-circuit voltage and the internal quasi-Fermi level splitting (QFLS), the transport resistance-free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity-dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non-radiative fill factor and open-circuit voltage loss. It is found that potassium-passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1434 KW - non-radiative interface recombination KW - perovskite solar cells KW - photoluminescence Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-516622 SN - 1866-8372 IS - 17 ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Grischek, Max A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Gutierrez-Partida, Emilio A1 - Peña-Camargo, Francisco A1 - Rothhardt, Daniel A1 - Zhang, Shanshan A1 - Raoufi, Meysam A1 - Wolansky, Jakob A1 - Abdi-Jalebi, Mojtaba A1 - Stranks, Samuel D. A1 - Albrecht, Steve A1 - Kirchartz, Thomas A1 - Neher, Dieter T1 - How to quantify the efficiency potential of neat perovskite films BT - Perovskite semiconductors with an implied efficiency exceeding 28% JF - Advanced Materials N2 - Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are not limited by Auger recombination under 1-sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non-radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open-circuit voltage and the internal quasi-Fermi level splitting (QFLS), the transport resistance-free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity-dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non-radiative fill factor and open-circuit voltage loss. It is found that potassium-passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit. KW - non-radiative interface recombination KW - perovskite solar cells KW - photoluminescence Y1 - 2020 U6 - https://doi.org/10.1002/adma.202000080 SN - 0935-9648 SN - 1521-4095 VL - 32 IS - 17 SP - 1 EP - 10 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Zeiske, Stefan A1 - Sandberg, Oskar J. A1 - Zarrabi, Nasim A1 - Wolff, Christian Michael A1 - Raoufi, Meysam A1 - Peña-Camargo, Francisco A1 - Gutierrez-Partida, Emilio A1 - Meredith, Paul A1 - Stolterfoht, Martin A1 - Armin, Ardalan T1 - Static disorder in lead halide perovskites JF - The journal of physical chemistry letters N2 - In crystalline and amorphous semiconductors, the temperature-dependent Urbach energy can be determined from the inverse slope of the logarithm of the absorption spectrum and reflects the static and dynamic energetic disorder. Using recent advances in the sensitivity of photocurrent spectroscopy methods, we elucidate the temperature-dependent Urbach energy in lead halide perovskites containing different numbers of cation components. We find Urbach energies at room temperature to be 13.0 +/- 1.0, 13.2 +/- 1.0, and 13.5 +/- 1.0 meV for single, double, and triple cation perovskite. Static, temperature-independent contributions to the Urbach energy are found to be as low as 5.1 ?+/- 0.5, 4.7 +/- 0.3, and 3.3 +/- 0.9 meV for the same systems. Our results suggest that, at a low temperature, the dominant static disorder in perovskites is derived from zero-point phonon energy rather than structural disorder. This is unusual for solution-processed semiconductors but broadens the potential application of perovskites further to quantum electronics and devices. KW - Cations KW - External quantum efficiency KW - Perovskites KW - Solar cells KW - Solar energy Y1 - 2022 U6 - https://doi.org/10.1021/acs.jpclett.2c01652 SN - 1948-7185 VL - 13 IS - 31 SP - 7280 EP - 7285 PB - American Chemical Society CY - Washington ER -