The tuning of interfacial properties at selective and desired locations on the particles is of great importance to create the novel structured particles by breaking the symmetry of their surface property. Herein, a dramatic transition of both the external shape and internal morphology of the particles of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) was induced by precise positioning of size-controlled Au nanoparticle surfactants (Au NPs). The size-dependent assembly of the Au NPs was localized preferentially at the interface between the P4VP domain at the particle surface and the surrounding water, which generated a balanced interfacial interaction between two different PS/P4VP domains of the BCP particles and water, producing unique convex lens-shaped BCP particles. In addition, the neutralized interfacial interaction, in combination with the directionality of the solvent-induced ordering of the BCP domains from the interface of the particle/water, generated defect-free, vertically ordered porous channels within the particles. The mechanism for the formation of these novel nanostructures was investigated systemically by varying the size and the volume fraction of the Au NPs. Furthermore, these convex lens-shaped particles with highly ordered channels can be used as a microlens, in which the light can be concentrated toward the focal point with enhanced near-field signals. And, these particles can possess additional optical properties such as unique distribution of light scattering as a result of the well-ordered Au cylinders that filled into the channels, which hold great promise for use in optical, biological-sensing, and imaging applications.

Colloidal particles with controlled shape and internal structure have attracted great attention due to their novel morphologies and various potential applications. Among the diverse synthetic strategies toward anisotropically shaped polymer particles, facile and accurate engineering of such structures remains challenging. This review highlights the synthetic approaches to manipulate the shape of polymer particles driven by phase separation in emulsions upon solvent evaporation. And, special attention is given to the thermodynamic and kinetic principles of particle shape control, followed by detailed experimental examples and their applications. Major synthetic strategies for the preparation of nonspherical block copolymer (BCP) particles by evaporation of solvent from BCP‐containing emulsions are discussed as follows: engineering of i) interfacial properties of the confining emulsion droplets, ii) particle (or droplet) size, iii) segregation behavior of BCPs within the droplet, and iv) solvent‐induced BCP self‐assembly kinetics (i.e., solvent evaporation rate). Next, functionalized BCP particles produced by careful design of the chemical structures of polymer or by incorporation of functional additives into the polymer matrix are introduced. Finally, this review article aims to present the challenging issues associated with current methods and future directions for research in this field.

Confined assembly of block copolymers (BCPs) is receiving increasing attention due to the ability to create unconventional morphologies that cannot be observed in the corresponding bulk systems. This effect is further driven by the simplicity and versatility of these procedures for controlling the shape of particles prepared by 3D soft confinement of BCPs in emulsions. By taking advantage of a mobile emulsion interface, the one-step formation of nonspherical BCP particles through spontaneous deformation is possible with design principles and theoretical models for controlling shape/nanostructure now being established. This Viewpoint highlights strategies for shape tuning of BCP particles, currently accessible shapes, their controllability, and potential application. The emergence of 3D soft confinement of BCPs and related theory is overviewed with a focus on current strategies, types of nonspherical shapes achieved, and structure–property relationships for nonspherical BCP particles. Finally, the applications and future perspectives for these materials are discussed.

Full-color reflective photonic ellipsoidal polymer particles, capable of a dynamic color change, are created from dendronized brush block copolymers (den-BBCPs) self-assembled by solvent-evaporation from an emulsion. Surfactants composed of dendritic monomer units allow for the precise modulation of the interfacial properties of den-BBCP particles to transition in shape from spheres to striped ellipsoids. Strong steric repulsions between wedge-type monomers promote rapid self-assembly of polymers into large domains (i.e., 153 nm ≤ D ≤ 298 nm). Of note, highly ordered axially stacked lamellae (i.e., number of layers > 100) within an ellipsoid give rise to a near-perfect photonic multilayer. The reflecting color is readily tunable across the entire visible spectrum by altering the molecular weight from 477 to 1144 kDa. Finally, the photonic ellipsoids are functionalized with magnetic nanoparticles organized into bands on the particle surface to produce real-time on/off coloration by magnetic field-assisted activation. In total the reported photonic ellipsoidal particles represent a new class of switchable photonic materials.

We report a simple and practical method for creating colloidal patchy particles with a variety of three-dimensional shapes via the evaporation-induced assembly of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) in an oil-in-water emulsion. Depending on the particle volume, a series of patchy particles in the shapes of snowmen, dumbbells, triangles, tetrahedra, and raspberry can be prepared, which are then precisely tuned by modulating the interfacial interaction at the particle/water interface using a mixture of two different surfactants. Moreover, for a given interfacial interaction, the stretching penalty of the BCPs in the patchy particles can be systematically controlled by adding P4VP homopolymers, which decreases the number of patches of soft particles from multiple patches to a single patch but increases the size of the patch. Calculations based on the strong segregation theory supported the experimental observation of various soft patchy particles and identified the underlying principles of their formation with tunable 3D structures.