Morphology Induced Spinodal Decomposition at the Surface of Symmetric Diblock Copolymer Films

Atomic force microscopy is used to study the ordering dynamics of symmetric diblock copolymer films. The films order to form a lamellar structure which results in a frustration when the film thickness is incommensurate with the lamellae. By probing the morphology of incommensurate films in the early ordering stages, we discover an intermediate phase of lamellae arranged perpendicular to the film surface. This morphology is accompanied by a continuous growth in amplitude of the film surface topography with a characteristic wavelength, indicative of a spinodal process. Using self-consistent field theory, we show that the observation of perpendicular lamellae suggests an intermediate state with parallel lamellae at the substrate and perpendicular lamellae at the free surface. The calculations confirm that the intermediate state is unstable to thickness fluctuations, thereby driving the spinodal growth of surface structures

Structure, Stability, and Reorganization of 0.5 <i>L</i>₀ Topography in Block Copolymer Thin Films

The structure, stability, and reorganization of lamella-forming block copolymer thin film surface topography (“islands” and “holes”) were studied under boundary conditions driving the formation of 0.5 <i>L</i>₀ thick structures at short thermal annealing times. Self-consistent field theory predicts that the presence of one perfectly neutral surface renders 0.5 <i>L</i>₀ topography thermodynamically stable relative to 1 <i>L</i>₀ thick features, in agreement with previous experimental observations. The calculated through-film structures match cross-sectional scanning electron micrographs, collectively demonstrating the pinning of edge dislocations at the neutral surface. Remarkably, near-neutral surface compositions exhibit 0.5 <i>L</i>₀ topography metastability upon extended thermal treatment, slowly transitioning to 1 <i>L</i>₀ islands or holes as evidenced by optical and atomic force microscopy. Surface restructuring is rationalized by invoking commensurability effects imposed by slightly preferential surfaces. The results described herein clarify the impact of interfacial interactions on block copolymer self-assembly and solidify an understanding of 0.5 <i>L</i>₀ topography, which is frequently used to determine neutral surface compositions of considerable importance to contemporary technological applications