Depth Profiling of Block Copolymer Nanostructures in Films by Small‐ A ngle X‐Ray Scattering Using an X‐ R ay Microbeam

Summary We applied the microbeam two‐dimensional small‐angle X‐ray scattering (2d‐ µ SAXS) technique in order to characterize orientation of polystyrene (PS) microdomains as a function of the distance from the free surface of a sample sheet down to the surface facing to the substrate, for depth profiling for spontaneous perpendicular orientation of PS cylinders in the matrix of polyethylenebutylene (PEB) in a PS‐ b ‐PEB‐ b ‐PS triblock copolymer thick sheet as thick as ∼0.5 mm. It has been revealed that near the free surface the cylinders were randomly oriented down to ∼70 µm in depth. Although this might indicate that the surface effect, which preferentially dictates cylinders to be oriented parallel to the surface, can propagate for such a long distance, 70 µm is unusually huge as compared to the general knowledge of the surface effect propagating at most for 1 µm. Experimentally examining further, we finally conclude that the 2d‐ µ SAXS depth profiling overestimates the surface effect. This unfavorable conclusion may be ascribed to surface roughness of the sample sheet subjected to the measurement, and in order to obtain a good result a big effort is required to prepare the surface as flat as possible.