TY - JOUR A1 - Wenz, Leonie A1 - Levermann, Anders A1 - Willner, Sven N. A1 - Otto, Christian A1 - Kuhla, Kilian T1 - Post-Brexit no-trade-deal scenario: short-term consumer benefit at the expense of long-term economic development JF - PLoS ONE N2 - After the United Kingdom has left the European Union it remains unclear whether the two parties can successfully negotiate and sign a trade agreement within the transition period. Ongoing negotiations, practical obstacles and resulting uncertainties make it highly unlikely that economic actors would be fully prepared to a “no-trade-deal” situation. Here we provide an economic shock simulation of the immediate aftermath of such a post-Brexit no-trade-deal scenario by computing the time evolution of more than 1.8 million interactions between more than 6,600 economic actors in the global trade network. We find an abrupt decline in the number of goods produced in the UK and the EU. This sudden output reduction is caused by drops in demand as customers on the respective other side of the Channel incorporate the new trade restriction into their decision-making. As a response, producers reduce prices in order to stimulate demand elsewhere. In the short term consumers benefit from lower prices but production value decreases with potentially severe socio-economic consequences in the longer term. KW - model KW - origins KW - chains KW - impact KW - costs Y1 - 2019 VL - 15 IS - 9 PB - PLOS CY - San Francisco 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 - 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 - Wunderling, Nico A1 - Willeit, Matteo A1 - Donges, Jonathan A1 - Winkelmann, Ricarda T1 - Global warming due to loss of large ice masses and Arctic summer sea ice JF - Nature Communications N2 - Several large-scale cryosphere elements such as the Arctic summer sea ice, the mountain glaciers, the Greenland and West Antarctic Ice Sheet have changed substantially during the last century due to anthropogenic global warming. However, the impacts of their possible future disintegration on global mean temperature (GMT) and climate feedbacks have not yet been comprehensively evaluated. Here, we quantify this response using an Earth system model of intermediate complexity. Overall, we find a median additional global warming of 0.43 degrees C (interquartile range: 0.39-0.46 degrees C) at a CO2 concentration of 400 ppm. Most of this response (55%) is caused by albedo changes, but lapse rate together with water vapour (30%) and cloud feedbacks (15%) also contribute significantly. While a decay of the ice sheets would occur on centennial to millennial time scales, the Arctic might become ice-free during summer within the 21st century. Our findings imply an additional increase of the GMT on intermediate to long time scales. The disintegration of cryosphere elements such as the Arctic summer sea ice, mountain glaciers, Greenland and West Antarctica is associated with temperature and radiative feedbacks. In this work, the authors quantify these feedbacks and find an additional global warming of 0.43 degrees C. Y1 - 2020 U6 - https://doi.org/10.1038/s41467-020-18934-3 SN - 2041-1723 VL - 11 IS - 1 PB - Nature Publishing Group CY - Berlin ER - TY - JOUR A1 - Xu, Pengbo A1 - Deng, Weihua A1 - Sandev, Trifce T1 - Levy walk with parameter dependent velocity BT - hermite polynomial approach and numerical simulation JF - Journal of physics : A, Mathematical and theoretical N2 - To analyze stochastic processes, one often uses integral transform (Fourier and Laplace) methods. However, for the time-space coupled cases, e.g. the Levy walk, sometimes the integral transform method may fail. Here we provide a Hermite polynomial expansion approach, being complementary to the integral transform method, to the Levy walk. Two approaches are compared for some already known results. We also consider the generalized Levy walk with parameter dependent velocity. Namely, we consider the Levy walk with velocity which depends on the walking length or on the duration of each step. Some interesting features of the generalized Levy walk are observed, including the special shapes of the probability density function, the first passage time distributions, and various diffusive behaviors of the mean squared displacement. KW - Hermite polynomial expansion KW - Levy walk KW - anomalous diffusion KW - parameter KW - dependent velocity Y1 - 2020 U6 - https://doi.org/10.1088/1751-8121/ab7420 SN - 1751-8113 SN - 1751-8121 VL - 53 IS - 11 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Xu, Pengbo A1 - Zhou, Tian A1 - Metzler, Ralf A1 - Deng, Weihua T1 - Lévy walk dynamics in an external harmonic potential JF - Physical review : E, Statistical, nonlinear, and soft matter physics N2 - Levy walks (LWs) are spatiotemporally coupled random-walk processes describing superdiffusive heat conduction in solids, propagation of light in disordered optical materials, motion of molecular motors in living cells, or motion of animals, humans, robots, and viruses. We here investigate a key feature of LWs-their response to an external harmonic potential. In this generic setting for confined motion we demonstrate that LWs equilibrate exponentially and may assume a bimodal stationary distribution. We also show that the stationary distribution has a horizontal slope next to a reflecting boundary placed at the origin, in contrast to correlated superdiffusive processes. Our results generalize LWs to confining forces and settle some longstanding puzzles around LWs. Y1 - 2020 U6 - https://doi.org/10.1103/PhysRevE.101.062127 SN - 2470-0045 SN - 2470-0053 SN - 1550-2376 SN - 1063-651X SN - 1539-3755 VL - 101 IS - 6 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Xu, Yong A1 - Liu, Xuemei A1 - Li, Yongge A1 - Metzler, Ralf T1 - Heterogeneous diffusion processes and nonergodicity with Gaussian colored noise in layered diffusivity landscapes JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - Heterogeneous diffusion processes (HDPs) with space-dependent diffusion coefficients D(x) are found in a number of real-world systems, such as for diffusion of macromolecules or submicron tracers in biological cells. Here, we examine HDPs in quenched-disorder systems with Gaussian colored noise (GCN) characterized by a diffusion coefficient with a power-law dependence on the particle position and with a spatially random scaling exponent. Typically, D(x) is considered to be centerd at the origin and the entire x axis is characterized by a single scaling exponent a. In this work we consider a spatially random scenario: in periodic intervals ("layers") in space D(x) is centerd to the midpoint of each interval. In each interval the scaling exponent alpha is randomly chosen from a Gaussian distribution. The effects of the variation of the scaling exponents, the periodicity of the domains ("layer thickness") of the diffusion coefficient in this stratified system, and the correlation time of the GCN are analyzed numerically in detail. We discuss the regimes of superdiffusion, subdiffusion, and normal diffusion realisable in this system. We observe and quantify the domains where nonergodic and non-Gaussian behaviors emerge in this system. Our results provide new insights into the understanding of weak ergodicity breaking for HDPs driven by colored noise, with potential applications in quenched layered systems, typical model systems for diffusion in biological cells and tissues, as well as for diffusion in geophysical systems. Y1 - 2020 U6 - https://doi.org/10.1103/PhysRevE.102.062106 SN - 2470-0045 SN - 2470-0053 VL - 102 IS - 6 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Yeste, Maria Pilar A1 - Primus, Philipp-Alexander A1 - Alcantara, Rodrigo A1 - Cauqui, Miguel Angel A1 - Calvino, Juan Jose A1 - Pintado, José María A1 - Blanco, Ginesa T1 - Surface characterization of two Ce0.62Zr0.38O2 mixed oxides with different reducibility JF - Applied surface science : a journal devoted to applied physics and chemistry of surfaces and interfaces N2 - This paper presents a study of the surface properties of two Ce/Zr mixed oxides with different reducibility, obtained by applying distinct thermal ageing treatments to an oxide with the composition Ce0.62Zr0.38O2. The surface composition was investigated by XPS. Chemical reactivity of the surface was studied by adsorption of the probe molecules CO2, D-2 and methanol. Nanostructural characterization was carried out by XRD, Raman and high-resolution Eu3+ spectroscopy (FLNS). The characterization showed only slight variations in surface composition and bulk Ce-Zr distribution, but hardy differences concerning the type and strength of acidic surface centres, as well as strong differences in the ability to dissociate hydrogen. Structural variations between both samples were identified by comparing the optical spectra of Eu3+ in surface doped samples. KW - Ce/Zr KW - Surface properties KW - Reactive adsorption KW - Hydrogen activation Y1 - 2020 U6 - https://doi.org/10.1016/j.apsusc.2019.144255 SN - 0169-4332 SN - 1873-5584 VL - 503 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Yochelis, Arik A1 - Beta, Carsten A1 - Gov, Nir S. T1 - Excitable solitons BT - annihilation, crossover, and nucleation of pulses in mass-conserving activator-inhibitor media JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - Excitable pulses are among the most widespread dynamical patterns that occur in many different systems, ranging from biological cells to chemical reactions and ecological populations. Traditionally, the mutual annihilation of two colliding pulses is regarded as their prototypical signature. Here we show that colliding excitable pulses may exhibit solitonlike crossover and pulse nucleation if the system obeys a mass conservation constraint. In contrast to previous observations in systems without mass conservation, these alternative collision scenarios are robustly observed over a wide range of parameters. We demonstrate our findings using a model of intracellular actin waves since, on time scales of wave propagations over the cell scale, cells obey conservation of actin monomers. The results provide a key concept to understand the ubiquitous occurrence of actin waves in cells, suggesting why they are so common, and why their dynamics is robust and long-lived. Y1 - 2020 U6 - https://doi.org/10.1103/PhysRevE.101.022213 SN - 2470-0045 SN - 2470-0053 VL - 101 IS - 2 PB - American Physical Society CY - Melville, NY ER - TY - JOUR A1 - Zeitz, Maria A1 - Levermann, Anders A1 - Winkelmann, Ricarda T1 - Sensitivity of ice loss to uncertainty in flow law parameters in an idealized one-dimensional geometry JF - The Cryosphere : TC ; an interactive open access journal of the European Geosciences Union N2 - Acceleration of the flow of ice drives mass losses in both the Antarctic and the Greenland Ice Sheet. The projections of possible future sea-level rise rely on numerical ice-sheet models, which solve the physics of ice flow, melt, and calving. While major advancements have been made by the ice-sheet modeling community in addressing several of the related uncertainties, the flow law, which is at the center of most process-based ice-sheet models, is not in the focus of the current scientific debate. However, recent studies show that the flow law parameters are highly uncertain and might be different from the widely accepted standard values. Here, we use an idealized flow-line setup to investigate how these uncertainties in the flow law translate into uncertainties in flow-driven mass loss. In order to disentangle the effect of future warming on the ice flow from other effects, we perform a suite of experiments with the Parallel Ice Sheet Model (PISM), deliberately excluding changes in the surface mass balance. We find that changes in the flow parameters within the observed range can lead up to a doubling of the flow-driven mass loss within the first centuries of warming, compared to standard parameters. The spread of ice loss due to the uncertainty in flow parameters is on the same order of magnitude as the increase in mass loss due to surface warming. While this study focuses on an idealized flow-line geometry, it is likely that this uncertainty carries over to realistic three-dimensional simulations of Greenland and Antarctica. Y1 - 2020 U6 - https://doi.org/10.5194/tc-14-3537-2020 SN - 1994-0416 SN - 1994-0424 VL - 14 IS - 10 SP - 3537 EP - 3550 PB - Copernicus CY - Göttingen ER - TY - JOUR A1 - Zhong, Yufei A1 - Causa, Martina A1 - Moore, Gareth John A1 - Krauspe, Philipp A1 - Xiao, Bo A1 - Günther, Florian A1 - Kublitski, Jonas A1 - BarOr, Eyal A1 - Zhou, Erjun A1 - Banerji, Natalie T1 - Sub-picosecond charge-transfer at near-zero driving force in polymer:non-fullerene acceptor blends and bilayers JF - Nature Communications N2 - Organic photovoltaics based on non-fullerene acceptors (NFAs) show record efficiency of 16 to 17% and increased photovoltage owing to the low driving force for interfacial charge-transfer. However, the low driving force potentially slows down charge generation, leading to a tradeoff between voltage and current. Here, we disentangle the intrinsic charge-transfer rates from morphology-dependent exciton diffusion for a series of polymer:NFA systems. Moreover, we establish the influence of the interfacial energetics on the electron and hole transfer rates separately. We demonstrate that charge-transfer timescales remain at a few hundred femtoseconds even at near-zero driving force, which is consistent with the rates predicted by Marcus theory in the normal region, at moderate electronic coupling and at low re-organization energy. Thus, in the design of highly efficient devices, the energy offset at the donor:acceptor interface can be minimized without jeopardizing the charge-transfer rate and without concerns about a current-voltage tradeoff. KW - organic solar cell KW - electron-transfer KW - Donor-Acceptor (DA) interface KW - transfer dynamics KW - donor KW - seperation KW - efficiency KW - impact KW - energy KW - photovoltaics Y1 - 2020 U6 - https://doi.org/10.1038/s41467-020-14549-w SN - 2041-1723 VL - 11 IS - 1 SP - 1 EP - 10 PB - Nature Publishing Group UK CY - London ER - TY - GEN A1 - Zhong, Yufei A1 - Causa, Martina A1 - Moore, Gareth John A1 - Krauspe, Philipp A1 - Xiao, Bo A1 - Günther, Florian A1 - Kublitski, Jonas A1 - BarOr, Eyal A1 - Zhou, Erjun A1 - Banerji, Natalie T1 - Sub-picosecond charge-transfer at near-zero driving force in polymer:non-fullerene acceptor blends and bilayers T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Organic photovoltaics based on non-fullerene acceptors (NFAs) show record efficiency of 16 to 17% and increased photovoltage owing to the low driving force for interfacial charge-transfer. However, the low driving force potentially slows down charge generation, leading to a tradeoff between voltage and current. Here, we disentangle the intrinsic charge-transfer rates from morphology-dependent exciton diffusion for a series of polymer:NFA systems. Moreover, we establish the influence of the interfacial energetics on the electron and hole transfer rates separately. We demonstrate that charge-transfer timescales remain at a few hundred femtoseconds even at near-zero driving force, which is consistent with the rates predicted by Marcus theory in the normal region, at moderate electronic coupling and at low re-organization energy. Thus, in the design of highly efficient devices, the energy offset at the donor:acceptor interface can be minimized without jeopardizing the charge-transfer rate and without concerns about a current-voltage tradeoff. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1422 KW - organic solar cell KW - electron-transfer KW - Donor-Acceptor (DA) interface KW - transfer dynamics KW - donor KW - seperation KW - efficiency KW - impact KW - energy KW - photovoltaics Y1 - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-511936 SN - 1866-8372 IS - 1 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 -