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.

Controlling the morphology of metal halide perovskite layers during processing is critical for the manufacturing of optoelectronics. Here, a strategy to control the microstructure of solution‐processed layered Ruddlesden–Popper‐phase perovskite films based on phenethylammonium lead bromide ((PEA)2PbBr4) is reported. The method relies on the addition of the organic semiconductor 2,7‐dioctyl[1]benzothieno[3,2‐b]benzothiophene (C8‐BTBT) into the perovskite formulation, where it facilitates the formation of large, near‐single‐crystalline‐quality platelet‐like (PEA)2PbBr4 domains overlaid by a ≈5‐nm‐thin C8‐BTBT layer. Transistors with (PEA)2PbBr4/C8‐BTBT channels exhibit an unexpectedly large hysteresis window between forward and return bias sweeps. Material and device analysis combined with theoretical calculations suggest that the C8‐BTBT‐rich phase acts as the hole‐transporting channel, while the quantum wells in (PEA)2PbBr4 act as the charge storage element where carriers from the channel are injected, stored, or extracted via tunneling. When tested as a non‐volatile memory, the devices exhibit a record memory window (>180 V), a high erase/write channel current ratio (104), good data retention, and high endurance (>104 cycles). The results here highlight a new memory device concept for application in large‐area electronics, while the growth technique can potentially be exploited for the development of other optoelectronic devices including solar cells, photodetectors, and light‐emitting diodes.

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.

Engineering the energetics of perovskite photovoltaic devices through the deliberate introduction of dipoles to control the built-in potential of the devices offers the opportunity to enhance their performance without the need to modify the active layer itself. In this work, we demonstrate how the incorporation of molecular dipoles into the bathocuproine (BCP) hole-blocking layer of inverted perovskite solar cells improves the device open-circuit voltage (VOC) and consequently, its performance. We explore a series of four thiaazulenic derivatives that exhibit increasing dipole moments and demonstrate that these molecules can be introduced into the solution-processed BCP layer to effectively increase the built-in potential within the device, without altering any of the other device layers. As a result the VOC of the devices is enhanced by up to 130 mV with larger dipoles resulting in higher VOCs. To investigate the limitations of this approach, we employ numerical device simulations that demonstrate that the highest dipole derivatives used in this work eliminate all limitations on the VOC stemming from the built-in potential of the device.