the donor-acceptor ratio, [7][8][9] the molecular weight, [10][11][12][13] side-chain engineering, [14][15][16] choice of solvent, [17][18][19] fl uorine substitution, [ 20 ] solvent mixtures, [ 21 ] additives, [ 22,23 ] solvent, [ 21,[24][25][26][27] and thermal annealing. [ 28 ] Although the power conversion effi ciency (PCE) of organic BHJ solar cells continues to increase, there has been a growing interest in quantifying the mechanisms and morphology that affect device performance. [29][30][31][32][33][34] Given that many factors infl uence the photovoltaic performance of BHJ devices via charge generation and extraction, it has often been very diffi cult to deduce explicit correlations between a change in morphology and an observed variation in device performance, let alone offer straightforward yet convincing physical causes. Hence, a deeper understanding of these processes may enable the design of materials that are more effi cient and would aid future commercialization efforts.For most BHJ systems, improved solar cell performance has been achieved by varying the fi lm processing conditions often leading to a distinctly different morphology from those seen in lower performing devices. This has led to the model and expectation that pure domains with lateral in-plane dimensions of ≈10 nm need to be matched with the exciton diffusion length alongside high electron as well as hole mobilities. [ 20,35 ] It has also been shown that in bilayer model systems with single planar heterojunctions as well as in polymer-fullerene BHJs the degree of preferential molecular orientation relative to donor-acceptor interface is strongly correlated with the shortcircuit current ( J sc ) and fi ll factor ( FF ). [36][37][38] More recently, it was reported that the miscibility of the fullerene in the donor can be considerable and the mixed component domains lead to excellent exciton quenching and charge generation. [38][39][40][41][42][43][44][45][46][47] The actual morphologies might thus comprise three phases, with relatively pure, aggregated donor and acceptor domains in addition to mixed amorphous regions, as shown in Figure 1 . It has been suggested that indeed this three phase morphology may be favorable as the electronic structure of both the donor and acceptor depends on the level of aggregation, thus providing an electronic landscape that can help to sweep charges out of the mixed domains. [ 33,[48][49][50] Recent studies on polymer:fullerene systems reveal that average domain purity of the mixed phase