No abstract

Understanding the photophysics of charge generation in organic semiconductors is a critical step toward the further optimization of organic solar cells. The separation of electron–hole pairs in systems with large energy offsets is relatively well-understood; however, the photophysics in blends with low driving energy remains unclear. Herein, we use the material system PffBT4T-2OD:PC71BM as an example to show that the built-in electric field plays a critical role toward long-range charge separation in high-performance devices. By using steady-state and time-resolved spectroscopic techniques, we show that in neat films an energetic barrier impedes polymer exciton dissociation, preventing charge transfer to the fullerene acceptor. In complete devices, this barrier is diminished due to the built-in electric field provided by the interlayers/contacts and accompanying space-charge distribution. The observed behavior could also be relevant to other systems with low driving energy and emphasizes the importance of using complete devices, rather than solely films, for photophysical studies.

Four π‐extended phosphoniumfluorene electrolytes (π‐PFEs) are introduced as hole‐blocking layers (HBL) in inverted architecture planar perovskite solar cells with the structure of ITO/PEDOT:PSS/MAPbI3/PCBM/HBL/Ag. The deep‐lying highest occupied molecular orbital energy level of the π‐PFEs effectively blocks holes, decreasing contact recombination. It is demonstrated that the incorporation of π‐PFEs introduces a dipole moment at the PCBM/Ag interface, resulting in significant enhancement of the built‐in potential of the device. This enhancement results in an increase in the open‐circuit voltage of the device by up to 120 mV, when compared to the commonly used bathocuproine HBL. The results are confirmed both experimentally and by numerical simulation. This work demonstrates that interfacial engineering of the transport layer/contact interface by small molecule electrolytes is a promising route to suppress nonradiative recombination in perovskite devices and compensates for a nonideal energetic alignment at the hole‐transport layer/perovskite interface.

Despite tremendous advances in improving the efficiency of organic solar cells above 14%, the environmental stability of such devices remains an essential and widely inadequately addressed challenge. Understanding the underlying principles of device degradation is a critical step toward further development and commercialization of organic photovoltaics. Herein, we report on the effect of oxygen exposure on the operation and degradation of highly efficient PffBT4T-2OD:PC 71 BM photovoltaic devices. Ultrafast pump−probe transient absorption (TA) measurements and ultrasensitive photothermal deflection spectroscopy (PDS) in combination with field-effect transistors suggest that oxygen-induced doping of the active layer is responsible for the severe degradation of the photovoltaic performance. We find that light exposure further accelerates this effect without causing photo-oxidation of the materials.

Despite many advances toward improving the stability of organic photovoltaic devices, environmental degradation under ambient conditions remains a challenging obstacle for future application. Particularly conventional systems employing fullerene derivatives are prone to oxidize under illumination, limiting their applicability. Here, the environmental stability of the small molecule donor DRCN5T together with the fullerene acceptor PC 70 BM is reported. It is found that this system exhibits exceptional device stability, mainly due to almost constant short-circuit current. By employing ultrafast femtosecond transient absorption spectroscopy, this remarkable stability is attributed to two separate mechanisms: 1) DRCN5T exhibits high intrinsic resistance toward external factors, showing no signs of deterioration.2) The highly sensitive PC 70 BM is stabilized against degradation by the presence of DRCN5T through ultrafast, long-range energy transfer to the donor, rapidly quenching the fullerene excited states which are otherwise precursors for chemical oxidation. It is proposed that this photoprotective mechanism be utilized to improve the device stability of other systems, including nonfullerene acceptors and ternary blends.

Energy level diagrams in organic electronic devices play a crucial role in device performance and interpretation of device physics. In the case of organic solar cells, it has become routine to estimate the photovoltaic gap of the donor:acceptor blend using the energy values measured on the individual blend components, resulting in a poor agreement with the corresponding open-circuit voltage of the device. To address this issue, we developed a method that allows a direct visualisation of the vertical energetic landscape in the blend, obtained by combining ultraviolet photoemission spectroscopy and argon cluster etching. We investigate both model and high-performance photovoltaic systems and demonstrate that the resulting photovoltaic gaps are in close agreement with the measured CT energies and open-circuit voltages. Furthermore, we show that this method allows us to study the evolution of the energetic landscape upon environmental degradation, critically important for understanding degradation mechanisms and development of mitigation strategies.

No abstract

In article number 1901257, Yana Vaynzof and co‐workers introduce π‐extended phosphoniumfluorene electrolytes as hole‐blocking layers in planar perovskite solar cells. The electrolytes drastically alter the energetic landscape of the device, introducing a strong dipole between the fullerene electron extraction layer and the silver electrode. This results in a substantial enhancement in the built‐in potential of the device, increasing its open‐circuit voltage by up to 120 meV.