The PM6:Y6 bulk-heterojunction (BHJ) blend system achieves high short-circuit current (J_SC) values in thick photovoltaic junctions. Here we analyse these solar cells to understand the observed independence of the short-circuit current upon photoactive layer thickness. We employ a range of optoelectronic measurements and analyses, including Mott–Schottky analysis, CELIV, photoinduced absorption spectroscopy, mobility measurements and simulations, to conclude that, the invariant photocurrent for the devices with different active layer thicknesses is associated with the Y6's diffusion length exceeding 300 nm in case of a 300 nm thick cell. This is despite unintentional doping that occurs in PM6 and the associated space-charge effect, which is expected to be even more profound upon photogeneration. This extraordinarily long diffusion length – which is an order of magnitude larger than typical values for organics – dominates transport in the flat-band region of thick junctions. Our work suggests that the performance of the doped PM6:Y6 organic solar cells resembles that of inorganic devices with diffusion transport playing a pivotal role. Ultimately, this is expected to be a key requirement for the fabrication of efficient, high-photocurrent, thick organic solar cells.

The choice of electrode for organic photovoltaics is known to be of importance to both device stability and performance, especially regarding the open-circuit voltage ($V_{\mathrm{OC}}$). Here we show that the work function of a nickel oxide anode, varied using an ${\mathrm{O}}_2$ plasma treatment, has a considerable influence on the open-circuit voltage $V_{\mathrm{OC}}$ of an organic solar cell. We probe recombination in the devices using transient photovoltage and charge extraction to determine the lifetime as a function of charge-carrier concentration and compare the experimental results with numerical drift-diffusion simulations. This combination of experiment and simulations allows us to conclude that the variations in $V_{\mathrm{OC}}$ are due to a change in surface recombination, localized at the NiO anode, although only a small change in carrier lifetime is observed.

Increasing the active layer thickness without sacrificing the power conversion efficiency (PCE) is one of the great challenges faced by organic solar cells (OSCs) for commercialization. Recently, PM6:Y6 as an OSC based on a non‐fullerene acceptor (NFA) has excited the community because of its PCE reaching as high as 15.9%; however, by increasing the thickness, the PCE drops due to the reduction of the fill factor (FF). This drop is attributed to change in mobility ratio with increasing thickness. Furthermore, this work demonstrates that by regulating the packing and the crystallinity of the donor and the acceptor, through volumetric content of chloronaphthalene (CN) as a solvent additive, one can improve the FF of a thick PM6:Y6 device (≈400 nm) from 58% to 68% (PCE enhances from 12.2% to 14.4%). The data indicate that the origin of this enhancement is the reduction of the structural and energetic disorders in the thick device with 1.5% CN compared with 0.5% CN. This correlates with improved electron and hole mobilities and a 50% suppressed bimolecular recombination, such that the non‐Langevin reduction factor is 180 times. This work reveals the role of disorder on the charge extraction and bimolecular recombination of NFA‐based OSCs.

The built-in voltage (V_BI) is a key parameter for solar cell operation, yet in perovskite solar cells the distribution, magnitude, and origin of the V_BI remains poorly understood. In this work, we systematically studied the V_BI in pin-type perovskite solar cells based on different hole transport layers (TLs). To this end, we determine the surface photovoltage (SPV) of partial and complete device stacks layer-by-layer by measuring the work function (WF) under dark and light (equivalent AM1.5G) conditions with Kelvin probe (KP) and photoemission spectroscopy (UPS) measurements in 3 different laboratories. We demonstrate that the SPV increases upon the addition of each additional layer until it equals the open-circuit voltage (V_OC) of the full device. This suggests that both the electron and hole transport layer (HTL/ETL) enlarge the SPV, by improving the separation of photogenerated carriers. Yet, the contribution of both transport layers to the total SPV of the device is small (in the range of ≈100 to 200 meV) and the largest contribution to the SPV originates from the top metal electrode (≈500 meV). The results suggest that the V_BI of pin-type perovskite solar cells is largely a result of the work-function difference of the electrodes. With regard to films (or incomplete cell stacks), our simulations can reproduce the measured SPV, and measured quasi-Fermi level splitting (>V_OC) in partial cell stacks without a significant internal field consistent with the experimental data. This work establishes layer-by-layer SPV measurements, which are easily accessible, as a key tool for understanding device performance and internal energetics, similar to layer-by-layer QFLS measurements.