We have experimentally determined a phase diagram for cylinder-forming polystyrene-block-polybutadien-block-polystyrene triblock copolymer in thin films. The phase behavior can be modeled in great detail by dynamic density functional theory. Deviations from the bulk structure, such as wetting layer, perforated lamella, and lamella, are identified as surface reconstructions. Their stability regions are determined by an interplay between surface fields and confinement effects.

Identification of energy-dissipation processes at the nanoscale is demonstrated by using amplitude-modulation atomic force microscopy. The variation of the energy dissipated on a surface by a vibrating tip as a function of its oscillation amplitude has a shape that singles out the dissipative process occurring at the surface. The method is illustrated by calculating the energy-dissipation curves for surface energy hysteresis, long-range interfacial interactions and viscoelasticity. The method remains valid with independency of the amount of dissipated energy per cycle, from 0.1 to 50 eV. The agreement obtained between theory and experiments performed on silicon and polystyrene validates the method.

We experimentally establish a phase diagram of thin films of concentrated solutions of a cylinder forming polystyrene-block-polybutadiene-block-polystyrene triblock copolymer in chloroform. During annealing the film forms islands and holes with energetically favored values of film thickness. The thin film structure depends on the local thickness of the film and the polymer concentration. Typically, at a thickness close to a favored film thickness parallel orientation of cylinders is observed, while perpendicular orientation is formed at an intermediate film thickness. At high polymer concentration the cylindrical microdomains reconstruct to a perforated lamella structure. Deviations from the bulk structure, such as the perforated lamella and a wetting layer are stabilized in films thinner than approximately 1.5 domain spacings.

The phase behavior of cylinder-forming ABA block copolymers in thin films is modeled in detail using dynamic density functional theory and compared with recent experiments on polystyrene-block-polybutadiene-block-polystyrene triblock copolymers. Deviations from the bulk structure, such as wetting layer, perforated lamella, and lamella, are identified as surface reconstructions. Their stability regions are determined by an interplay between surface fields and confinement effects. Our results give evidence for a general mechanism governing the phase behavior in thin films of modulated phases.

Microscopists have always pursued the development of an instrument that combines topography and materials properties analyses at the highest resolution. The measurement of the tiny amount of energy dissipated by a vibrating tip in the proximity of the sample surface has provided atomic force microscopes with a robust and versatile method to determine the morphology and the compositional variations of surfaces in their natural environment. Applications in biology, polymer science and microelectronics illustrate the potential of phase-imaging force microscopy for nanoscale analysis.

We have studied the microdomain morphology of thin ABC triblock copolymer films supported by a solid substrate. The films were exposed to various solvent vapors, and the effect of the solvent removal speed on the resulting morphologies is investigated. Slow solvent extraction rates lead to a parallel alignment of lamellar microphases within the plane of the film. On fast drying, a perpendicular orientation of the lamellae is found. In the case of block copolymer samples with a highly anisotropic macroscopic shape, the microdomains can be aligned over large lateral areas. The results are discussed in view of the mechanical strain fields present during the drying process.

We investigate in detail the processes involved when soft polymeric materials are imaged with TappingMode atomic force microscopy (TM-AFM). Measuring lateral arrays of amplitude/phase vs distance (APD) curves, we are able to determine quantitatively the amount of tip indentation and reconstruct the shape of the "real" surface of the sample. Moreover, contrast inversion in height and TappingMode phase images is explained on the basis of attractive and repulsive contributions to the tip-sample interaction. The experiments are performed on surfaces of poly(styrene-block-butadiene-blockstyrene) (SBS) triblock copolymers acting as a model system.

Thin films of incompatible block copolymers self‐assemble into highly regular supramolecular structures with characteristic dimensions in the 10–100 nm regime. There is increasing interest in controlling the resulting structures and utilizing them, for instance in the area of nanotechnology. So far, research has concentrated mainly on exploiting the melt structure of diblock copolymers. Recent work on block copolymer solutions and more complex co‐ and terpolymer architectures has revealed a rich variety of novel thin‐film structures, some of which exhibit high complexity and order. In addition, by use of mean field dynamic density functional theory along with well‐controlled experiments, the fundamentals of thin film structure formation have been elucidated. We highlight some aspects of these studies and point to future directions in this lively field of materials science.