The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to ‘manufacturability'. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the ‘anisotropic elasticity' across the particle–polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies.

The effect of polymer modification on the deformation characteristics and processibility of particle assembly structures is analyzed as a function of particle size and degree of polymerization of surface-tethered chains. A pronounced increase of the fracture toughness (by approximately one order of magnitude) is observed as the degree of polymerization exceeds a threshold value that increases with particle size. The threshold value is interpreted as being related to the transition of tethered chains from stretched-to-relaxed conformation (and the associated entanglement of tethered chains) and agrees with predictions from scaling theory. The increase in toughness is reduced with increasing particle size - this effect is rationalized as a consequence of the decrease of entanglement density with increasing dimension of interstitial (void) space in particle array structures. The increased fracture toughness of particle brush materials (with sufficient degree of polymerization of tethered chains) enables the fabrication of ordered colloidal films and even complex 3D shapes by scalable polymer processing techniques, such as spin coating and micromolding. The results, therefore, suggest new opportunities for the processing of colloidal material systems that could find application in the economical fabrication of functional components or systems compromised of colloidal materials.