Colloidal lithography is a recently emerging field; the evolution of this simple technique is still in progress. Recent advances in this area have developed a variety of practical routes of colloidal lithography, which have great potential to replace, at least partially, complex and high-cost advanced lithographic techniques. This Review presents the state of the art of colloidal lithography and consists of three main parts, beginning with synthetic routes to monodisperse colloids and their self-assembly with low defect concentrations, which are used as lithographic masks. Then, we will introduce the modification of the colloidal masks using reactive ion etching (RIE), which produces a variety of nanoscopic features and multifaceted particles. Finally, a few prospective applications of colloidal lithography will be discussed.

Control of interfacial interactions leads to a dramatic change in shape and morphology for particles based on poly(styrene-b-2-vinylpyridine) diblock copolymers. Key to these changes is the addition of Au-based surfactant nanoparticles (SNPs) which are adsorbed at the interface between block copolymer-containing emulsion droplets and the surrounding amphiphilic surfactant to afford asymmetric, ellipsoid particles. The mechanism of formation for these novel nanostructures was investigated by systematically varying the volume fraction of SNPs, with the results showing the critical nature that the segregation of SNPs to specific interfaces plays in controlling structure. A theoretical description of the system allows the size distribution and aspect ratio of the asymmetric block copolymer colloidal particles to be correlated with the experimental results.

We herein report a new facile strategy to ellipsoidal block copolymer nanoparticles exhibiting a pH-triggered anistropic swelling profile. In a first step, elongated particles with an axially stacked lamellae structure are selectively prepared by utilizing functional surfactants to control the phase separation of symmetric PS-b-P2VP in dispersed droplets. In a second step, the dynamic shape change is realized by crosslinking the P2VP domains, hereby connecting glassy PS discs with pH-sensitive hydrogel actuators.

A simple strategy to tailor the surface of nanoparticles for their specific adsorption to and localization at block copolymer interfaces was explored. Gold nanoparticles coated by a mixture of low molecular weight thiol end-functional polystyrene (PS-SH) (Mn = 1.5 and 3.4 kg/mol) and poly(2-vinylpyridine) homopolymers (P2VP-SH) (Mn = 1.5 and 3.0 kg/mol) were incorporated into a lamellar poly(styrene-b-2-vinylpyridine) diblock copolymer (PS-b-P2VP) (Mn = 196 kg/mol). A library of nanoparticles with varying PS and P2VP surface compositions (FPS) and high polymer ligand areal chain densities was synthesized. The location of the nanoparticles in the PS-b-P2VP block copolymer was determined by transmission electron microscopy. Sharp transitions in particle location from the PS domain to the PS/P2VP interface, and subsequently to the P2VP domain, were observed at FPS = 0.9 and 0.1, respectively. This extremely wide window of FPS values where the polymer-coated gold nanoparticles adsorb to the interface suggests a redistribution of PS and P2VP polymers on the Au surface, inducing the formation of amphiphilic nanoparticles at the PS/P2VP interface. In a second and synthetically more challenging approach, gold nanoparticles were covered with a thiol terminated random copolymer of styrene and 2-vinylpyridine synthesized by RAFT polymerization. Two different random copolymers were considered, where the molecular weight was fixed at 3.5 kg/mol and the relative incorporation of styrene and 2-vinylpyridine repeat units varied (FPS = 0.52 and 0.40). The areal chain density of these random copolymers on Au is unfortunately not high enough to preclude any contact between the P2VP block of the block copolymer and the Au surface. Interestingly, gold nanoparticles coated by the random copolymer with FPS = 0.4 were dispersed in the P2VP domain, while those with FPS = 0.52 were located at the interface. A simple calculation for the adsorption energy to the interface of the nanoparticles with different surface arrangements of PS and P2VP ligands supports evidence for the rearrangement of thiol terminated homopolymers. An upper limit estimate of the adsorption energy of nanoparticles uniformly coated with a random arrangement of PS and P2VP ligands where a 10% surface area was occupied by P2VP -mers or chains was approximately 1 kBT, which indicates that such nanoparticles are unlikely to be segregated along the interface, in contrast to the experimental results for nanoparticles with mixed ligand-coated surfaces.

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.

We report here a novel colloidal lithographic approach to the fabrication of nonspherical colloidal particle arrays with a long-range order by selective reactive ion etching (RIE) of multilayered spherical colloidal particles. First, layered colloidal crystals with different crystal structures (or orientations) were self-organized onto substrates. Then, during the RIE, the upper layer in the colloidal multilayer acted as a mask for the lower layer and the resulting anisotropic etching created nonspherical particle arrays and new patterns. The new patterns have shapes that are different from the original as a result of the relative shadowing of the RIE process by the top layer and the lower layers. The shape and size of the particles and patterns were dependent on the crystal orientation relative to the etchant flow, the number of colloidal layers, and the RIE conditions. The various colloidal patterns can be used as masks for two-dimensional (2-D) nanopatterns. In addition, the resulting nonspherical particles can be used as novel building blocks for colloidal photonic crystals.

High internal phase emulsions have been widely used as templates for various porous materials, but special strategies are required to form, in particular, particle-covered ones that have been more difficult to obtain. Here, we report a versatile strategy to produce a stable high internal phase Pickering emulsion by exploiting a depletion interaction between an emulsion droplet and a particle using water-soluble polymers as a depletant. This attractive interaction facilitating the adsorption of particles onto the droplet interface and simultaneously suppressing desorption once adsorbed. This technique can be universally applied to nearly any kind of particle to stabilize an interface with the help of various non- or weakly adsorbing polymers as a depletant, which can be solidified to provide porous materials for many applications.