AbstractUsing particle-based Monte Carlo simulations and continuum modeling, we study the self-assembly of asymmetric diblock copolymers in the course of solvent evaporation. We examine the effects of evaporation rate and solvent selectivity on the structure formation, especially the alignment of the cylindrical domains of the minority block. The comparison of the two simulation techniques facilitates identifying general trends upon parameter variation, while their inherent differences help us to understand the role of single-chain dynamics, fluctuations, and additional model details. In both cases, the simulation models feature a liquid and a gas phase with an explicit surface, across which solvent evaporates. We propose a “layer evolution model” that links processing parameters to the final morphology via the time dependence of layers, in which characteristic microphases, for example, spherical or cylindrical, can form. The evolution of these layers varies with the processing conditions and determines the morphology. This allows us to discuss the interplay of various experimentally accessible parameters, which we support by respective simulations. Our results single out two main factors to ensure the formation of minority-block cylinders, perpendicular to the film surface: (i) Fast evaporation rates induce a steep gradient in the polymer-density profile; that is, the polymer density immediately beneath the gas–liquid surface rapidly exceeds the critical value for cylinder formation. This confines cylinder formation into a layer that is thinner than the actual cylinder diameter, forcing a perpendicular alignment. (ii) A certain selectivity of the gas phase for the matrix-forming, majority block is necessary to disrupt an otherwise entropically favored surface layer of the minority block that would lead to parallel cylinder alignment.