Formation and dissolution of phase-separated structures in ultrathin blend films

The phase separation of ultrathin polymer blend films of deuterated poly(styrene)/poly(vinylmethylether) leads to a variety of film morphologies, depending on polymer composition. Phase-separation measurements are made at a constant temperature difference from the critical temperature, leading to a bicontinuous spinodal decomposition pattern for near-critical blend compositions and to “mounds” and “holes” for PVME-rich and dPS-rich off-critical mixtures, respectively. Reverse temperature jumps of the phase-separated blend films into the one-phase region result in dissolution of the undulating surface patterns, confirming the phase-separation origin of the film patterns.