Precisely shaped polymeric particles and structures are widely used for applications in photonic materials, MEMS, biomaterials and self-assembly. Current approaches for particle synthesis are either batch processes or flow-through microfluidic schemes that are based on two-phase systems, limiting the throughput, shape and functionality of the particles. We report a one-phase method that combines the advantages of microscope projection photolithography and microfluidics to continuously form morphologically complex or multifunctional particles down to the colloidal length scale. Exploiting the inhibition of free-radical polymerization near PDMS surfaces, we are able to repeatedly pattern and flow rows of particles in less than 0.1 s, affording a throughput of near 100 particles per second using the simplest of device designs. Polymerization was also carried out across laminar, co-flowing streams to generate Janus particles containing different chemistries, whose relative proportions could be easily tuned. This new high-throughput technique offers unprecedented control over particle size, shape and anisotropy.

Polymeric particles in custom designed geometries and with tunable chemical anisotropy are expected to enable a variety of new technologies in diverse areas such as photonics, diagnostics and functional materials. We present a simple, high throughput and high resolution microfluidic method to synthesize such polymeric particles. Building off earlier work that we have done on continuous flow lithography (CFL) (D. Dendukuri, D. C. Pregibon, J. Collins, T. A. Hatton, P. S. Doyle, Nat. Mater., 2006, 5, 365-369; ref. 1), we have devised and implemented a new setup that uses compressed air driven flows in preference to syringe pumps to synthesize particles using a technique that we call stop-flow lithography (SFL). A flowing stream of oligomer is stopped before polymerizing an array of particles into it, providing for much improved resolution over particles synthesized in flow. The formed particles are then flushed out at high flow rates before the cycle of stop-polymerize-flow is repeated. The high flow rates enable orders-of-magnitude improvements in particle throughput over CFL. However, the deformation of the PDMS elastomer due to the imposed pressure restricts how quickly the flow can be stopped before each polymerization event. We have developed a simple model that captures the dependence of the time required to stop the flow on geometric parameters such as the height, length and width of the microchannel, as well as on the externally imposed pressure. Further, we show that SFL proves to be superior to CFL even for the synthesis of chemically anisotropic particles with sharp interfaces between distinct sections.

The controlled synthesis of micrometer‐sized polymeric particles bearing features such as nonspherical shapes and spatially segregated chemical properties is becoming increasingly important. Such particles can enable fundamental studies on self‐assembly and suspension rheology, as well as be used in applications ranging from medical diagnostics to photonic devices. Microfluidics has recently emerged as a very promising route to the synthesis of such polymeric particles, providing fine control over particle shape, size, chemical anisotropy, porosity, and core/shell structure. This progress report summarizes microfluidic approaches to particle synthesis using both droplet‐ and flow‐lithography‐based methods, as well as particle assembly in microfluidic devices. The particles formed are classified according to their morphology, chemical anisotropy, and internal structure, and relevant examples are provided to illustrate each of these approaches. Emerging applications of the complex particles formed using these techniques and the outlook for such processes are discussed.

The controlled synthesis of nonspherical microparticles using microfluidics processing is described. Polymer droplets, formed by shearing a photopolymer using a continuous water phase at a T-junction, were constrained to adopt nonspherical shapes by confining them using appropriate microchannel geometries. Plugs were obtained by shearing the polymer phase at low shear rates, while disks were obtained by flattening droplets using a channel of low height. The nonspherical shapes formed were permanently preserved by photopolymerizing the constrained droplets in situ using ultraviolet light. Monodisperse plugs and disks of different lengths and diameters were obtained by varying the flow rates of the two phases.

Free-radical photopolymerization performed within PDMS microfluidic devices is now used for a variety of applications. We propose, through model and experiment, that atmospheric oxygen diffusing in through the porous PDMS is responsible for the presence, under UV light, of a thin, un-cross-linked film of oligomer abutting the walls of an all-PDMS device. After the advent of light exposure, an induction time τ i is required before the oxygen present in the oligomer is depleted, and cross-linking reactions can begin. A polymerized structure then grows from the center of the device outward, increasing sharply in height with time and leaving only a thin un-cross-linked film of thickness, δ i,c , close to the walls where oxygen can penetrate. Under suitable simplification of the reaction-diffusion model developed, scaling relationships were obtained for τ i (∼Da-1) and δ i,c (∼Da-1/2) as a function of a Damköhler number, Da. The relationships were successfully verified by comparison with both the full solution and experimental data. The analysis shows that control over particle height can be obtained more easily by changing initiator concentration, irradiation intensity, or channel height rather than exposure time.

Spherical and non-spherical magnetic hydrogel particles were synthesized in a microfluidic device containing an embedded UV light reflector. Monodisperse magnetic emulsion droplets were generated in a T-junction and allowed to relax into spheres, disks, and plugs in confining microchannel geometries. Particle morphology was locked-in via UV-initiated photopolymerization. The role of the reflector in the microchannel is to provide a uniform distribution of UV energy to the magnetic emulsion droplets and to increase the UV flux, which significantly improves UV polymerization conditions for microfluidic-based particle synthesis. Magnetic nanoparticles were uniformly encapsulated in the hydrogel, giving the microparticles superparamagnetic behavior. Additionally, the non-spherical particles show anisotropic responses under an applied external magnetic field.

We report the synthesis and self-assembly of amphiphilic, nonspherical, polymeric microparticles. Wedge-shaped particles bearing segregated hydrophilic and hydrophobic sections were synthesized in a microfludic channel by polymerizing across laminar coflowing streams of hydrophilic and hydrophobic polymers using continuous flow lithography (CFL). Particle monodispersity was characterized by measuring both the size of the particles formed and the extent of amphiphilicity. The coefficient of variation (COV) was found to be less than 2.5% in all measured dimensions. Particle structure was further characterized by measuring the curvature of the interface between the sections and the extent of cross-linking using FTIR spectroscopy. The amphiphilic particles were allowed to self-assemble in water or at water-oil interfaces. In water, the geometry of the particles enabled the formation of micelle-like structures, while in emulsions, the particles migrated to the oil-water interface and oriented themselves to minimize their surface energy.

Polymeric structures with repeating 2D and 3D motifs at the micrometer scale and below have a variety of uses. Patterned 2D structures have been shown to have myriad applications in biosensors, [1] tissue engineering, [2] and diagnostic assay systems.[3] The availability of more sophisticated 3D structures would enable important advances in photonics, [4] information storage, [5] and tissue engineering. [6,7] Many techniques have been developed to fabricate complex 3D structures at the micrometer scale and below using either top-down or bottomup approaches. Bottom-up approaches such as polymer phase separation, [8] molecular self-assembly, [9] or colloidal assembly [10] are cheap and can cover large areas but face defects and limitations in the type and the geometry of structures that can be formed. While top-down methods offer precise size and shape control, the necessary point-by-point or layer-by-layer processing makes methods such as gray-scale photolithography, [11] direct 3D writing, [12] or two-photon lithography [13] very time-consuming.Recently, interference lithography (IL) [14][15][16][17][18][19][20] has emerged as an attractive alternative technique that allows the rational design of complex and defect-free 1D, 2D, and 3D patterns over large areas. Besides being fast and efficient, IL also affords control over geometrical parameters, such as symmetry and volume fractions, of the structures formed. IL performed using an elastomeric poly(dimethylsiloxane) (PDMS) phase mask [17] has the further advantage of providing simple and cheap processing, since only a single collimated beam is needed to form 3D interference patterns. However, phase-mask interference lithography (PMIL) [15,17] is typically performed by flood exposing a spin-coated layer of photoresist film through a phase mask, thus imposing some restrictions on the shape and material properties of the structures formed as well as limiting the throughput because of the serial nature of processing. Furthermore, such processes are not easily amenable to the fabrication of chemically anisotropic structures. Chemical anisotropy refers to the presence of multiple segregated chemical functionalities or gradients of one or more chemical functionality in a structure.