Thermal Imaging of Block Copolymers with Sub-10 nm Resolution.

Thermal silicon probes have demonstrated their potential to investigate the thermal properties of various materials at high resolution. However, a thorough assessment of the achievable resolution is missing. Here, we present a probe-based thermal-imaging technique capable of providing sub-10 nm lateral resolution at a sub-10 ms pixel rate. We demonstrate the resolution by resolving microphase-separated PS-b-PMMA block copolymers that self-assemble in 11 to 19 nm half-period lamellar structures. We resolve an asymmetry in the heat flux signal at submolecular dimensions and assess the ratio of heat flux into both polymers in various geometries. These observations are quantitatively compared with coarse-grained molecular simulations of energy transport that reveal an enhancement of transport along the macromolecular backbone and a Kapitza resistance at the internal interfaces of the self-assembled structure. This comparison discloses a tip-sample contact radius of a ≈ 4 nm and identifies combinations of enhanced intramolecular transport and Kapitza resistance.

Interface Repulsion and Lamellar Structures in Thin Films of Homopolymer Blends due to Thermal Oscillations.

In equilibrium the interface potential that describes the interaction between two AB interfaces in a binary blend of A and B homopolymers is attractive at all distances, resulting in coarsening of the blend morphology even in the absence of interface curvature. We demonstrate that the dissipative assembly in response to a time-periodic variation of the blend incompatibility qualitatively alters this behavior; i.e., for suitable parameters the interface potential exhibits a periodic spatial modulation and AB interfaces adopt a well-defined distance. We explore for which oscillation periods and amplitudes an interface repulsion occurs and demonstrate that we can control the preferred interface distance over a wide range by varying the oscillation period. Using particle-based simulations we explicitly demonstrate that this dissipative assembly of a homopolymer blend results in a lamellar structure with multiple planar interfaces in a thin film geometry.