Nanoscale Q-Resolved Phonon Dynamics in Block Copolymers

In recent years, responsive polymer-based structures have been studied extensively due to their unique ability to alter their physical properties upon exposure to external stimuli. Despite this, the nanoscale Q-resolved dynamic properties of these materials have barely been explored, which is limiting the development and applications of these materials. To address this issue, we used inelastic X-ray scattering (IXS) and found evidence for van der Waals mediated molecular vibration-responsive rattling dynamics in bulk poly(isoprene-block-styrene) (SI) and poly(styrene-block-ethylene oxide) (SO) stacked thin film block copolymers. Their cylinder-forming hexagonally arranged static structures were characterized using small-angle X-ray scattering (SAXS) and grazing incidence small-angle X-ray scattering (GISAXS), complemented by scanning electron microscopy (SEM). Specifically, we observed that the longitudinal vibrational mode in bulk SI experiences a strong phonon attenuation as temperature increases from 30 to 90 °C, while the transverse phonon excitations are nonexistent in the measured Q-range due to anharmonicity-mediated symmetry breaking in phonon interactions. Furthermore, the emergent transverse acoustic phonon modes in both the bulk SI and SO thin films exhibited a nondispersive behavior with a nearly zero slope in the hydrodynamic limit (Q → 0), mimicking optical phonon excitations (i.e., standing waves). In summary, these findings point to the use of polymeric materials for Q-resolved nanoacoustic sensing, and the visualization of THz phonons.