Conjugated‐Polymer Blends for Organic Photovoltaics: Rational Control of Vertical Stratification for High Performance

The photoactive layer of bulk‐heterojunction organic solar cells, in a thickness range of tens to hundreds of nanometers, comprises phase‐separated electron donors and acceptors after solution casting. The component distribution in the cross‐section of these thin films is found to be heterogeneous, with electron donors or acceptors accumulated or depleted near the electrode interfaces. This vertical stratification of the photovoltaic blend influences device metrics through its impact on charge transport and recombination, and consequently plays an important role in determining the power conversion efficiency of photovoltaic devices. Here, different techniques, e.g., surface analysis and sputter‐assisted depth‐profiling, reflectivity modeling, and 3D imaging, that have been employed to characterize vertical stratification in bulk‐heterojunction photovoltaic blends are reviewed. The origins of vertical stratification are summarized, including thermodynamics, kinetics, surface free energy, and selective dissolubility. The impact of correct and wrong vertical stratification to device metrics of solar cells are highlighted. Examples are then given to demonstrate how desired vertical stratification can be controlled with properly aligned device architecture to enable solar cells with high efficiency.