Superlattices of polyhedral nanocrystals exhibit emergent properties defined by their structural arrangements, but native nanocrystal ligands often limit their programmability. Polymeric ligands address this limitation by enabling tunable nanocrystal softness through modifications of polymer molecular weight and grafting density. Here, we investigate phase transitions in polymer-grafted nanooctahedra by varying polymer length, nanocrystal size, truncation, and ligand density. In two-dimensional superlattices, longer polymers or smaller nanooctahedra induce a transition from orientationally ordered to hexagonal rotator lattices. In three-dimensional superlattices, increasing polymer length drives transitions from Minkowski to body-centered cubic and plastic hexagonal close-packed phases, while higher grafting densities further enable transitions to simple hexagonal phases. Polymer brush and thermodynamic perturbation theories, supported by Monte Carlo simulations, uncover the entropic and enthalpic forces that govern these transitions. This work highlights the versatility of polymer-grafted anisotropic nanocrystals as building blocks for designing hierarchical superstructures and metamaterials with customizable properties. 
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                            Architecture Controls Phonon Propagation in All‐Solid Brush Colloid Metamaterials
                        
                    
    
            Abstract Brillouin light scattering and elastodynamic theory are concurrently used to determine and interpret the hypersonic phonon dispersion relations in brush particle solids as a function of the grafting density with perspectives in optomechanics, heat management, and materials metrology. In the limit of sparse grafting density, the phonon dispersion relations bear similarity to polymer‐embedded colloidal assembly structures in which phonon dispersion can be rationalized on the basis of perfect boundary conditions, i.e., isotropic stiffness transitions across the particle interface. In contrast, for dense brush assemblies, more complex dispersion characteristics are observed that imply anisotropic stiffness transition across the particle/polymer interface. This provides direct experimental validation of phonon propagation changes associated with chain conformational transitions in dense particle brush materials. A scaling relation between interface tangential stiffness and crowding of polymer tethers is derived that provides a guideline for chemists to design brush particle materials with tailored phononic dispersion characteristics. The results emphasize the role of interfaces in composite materials systems. Given the fundamental relevance of phonon dispersion to material properties such as thermal transport or mechanical properties, it is also envisioned that the results will spur the development of novel functional hybrid materials. 
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                            - Award ID(s):
- 2209587
- PAR ID:
- 10519867
- Publisher / Repository:
- Wiley VCH GmbH
- Date Published:
- Journal Name:
- Small
- Volume:
- 20
- Issue:
- 13
- ISSN:
- 1613-6810
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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