Living systems are compelling evidence that multi scale, adaptive architectures can be built simply by letting their smallest parts self-organize as dictated by their intrinsic properties. 

Efforts to explain the mystery of self-assembly have ranged from “collective thinking” within continuously reconfiguring bird flocks to sophisticated algorithms describing how chains of local interactions can give rise to bacterial communities and cellular machinery. Yet we have little understanding of how to systematically encode such interactions directly into physical building blocks to track and control their assembly into arbitrary, dynamic structures, particularly at the nanoscale. 

Using periodic nanofiber arrays as both a model system and a starting point for fabricating optical, adhesive, and microfluidic materials, our group has demonstrated and developed a predictive theory for how to create elaborate helical, hierarchical structures simply by tweaking the mechanical, chemical, and geometric features of the fibers. Intriguingly, step-by-step examination of the process revealed an unexpected concept: the final structure is achieved through hierarchical stages of not only assembly but also disassembly.

Our continuing analysis of this latter phase suggests how, with a comprehensive understanding of the forces at play, building block features can be used to program selective, inducible top-down self-disassembly steps, giving the assembled structures a wide variety of dynamic, reversible, responsive behaviors. Yet another surprising self-assembly principle has come from our recent work on colloids: we have discovered that letting two different sets of building blocks co-assemble from the bottom up can enhance the long-range order of each by mutual correction of defects, and this too has led us to explore a new realm of possibilities for bottom-up creation of hierarchical architectures.

Kaplan CN, Wu N, Mandre S, Aizenberg J, Mahadevan L. Dynamics of evaporative colloidal patterning. Physics of Fluids [Internet]. 2015;27 (9) :092105. Full TextAbstract

Drying suspensions often leave behind complex patterns of particulates, as might be seen in the coffee stains on a table. Here, we consider the dynamics of periodic band or uniform solid film formation on a vertical plate suspended partially in a drying colloidal solution. Direct observations allow us to visualize the dynamics of band and film deposition, where both are made of multiple layers of close packed particles. We further see that there is a transition between banding and filming when the colloidal concentration is varied. A minimal theory of the liquid meniscus motion along the plate reveals the dynamics of the banding and its transition to the filming as a function of the ratio of deposition and evaporation rates. We also provide a complementary multiphase model of colloids dissolved in the liquid, which couples the inhomogeneous evaporation at the evolving meniscus to the fluid and particulate flows and the transition from a dilute suspension to a porous plug. This allows us to determine the concentration dependence of the bandwidth and the deposition rate. Together, our findings allow for the control of drying-induced patterning as a function of the colloidal concentration and evaporationrate.

Vogel N, Utech S, England GT, Shirman T, Phillips KR, Koay N, Burgess IB, Kolle M, Weitz DA, Aizenberg J. Color from hierarchy: Diverse optical properties of micron-sized spherical colloidal assemblies. Proc. Nat. Acad. Sci. [Internet]. 2015;112 (35) :10845-10850. Publisher's VersionAbstract
Materials in nature are characterized by structural order over multiple length scales have evolved for maximum performance and multifunctionality, and are often produced by self-assembly processes. A striking example of this design principle is structural coloration, where interference, diffraction, and absorption effects result in vivid colors. Mimicking this emergence of complex effects from simple building blocks is a key challenge for man-made materials. Here, we show that a simple confined self-assembly process leads to a complex hierarchical geometry that displays a variety of optical effects. Colloidal crystallization in an emulsion droplet creates micron-sized superstructures, termed photonic balls. The curvature imposed by the emulsion droplet leads to frustrated crystallization. We observe spherical colloidal crystals with ordered, crystalline layers and a disordered core. This geometry produces multiple optical effects. The ordered layers give rise to structural color from Bragg diffraction with limited angular dependence and unusual transmission due to the curved nature of the individual crystals. The disordered core contributes nonresonant scattering that induces a macroscopically whitish appearance, which we mitigate by incorporating absorbing gold nanoparticles that suppress scattering and macroscopically purify the color. With increasing size of the constituent colloidal particles, grating diffraction effects dominate, which result from order along the crystal’s curved surface and induce a vivid polychromatic appearance. The control of multiple optical effects induced by the hierarchical morphology in photonic balls paves the way to use them as building blocks for complex optical assemblies—potentially as more efficient mimics of structural color as it occurs in nature.
Schaffner M, England G, Kolle M, Aizenberg J, Vogel N. Combining Bottom-Up Self-Assembly with Top-Down Microfabrication to Create Hierarchical Inverse Opals with High Structural Order. Small [Internet]. 2015;11 (34) :4334-4340. Full TextAbstract
Colloidal particles can assemble into ordered crystals, creating periodically structured materials at the nanoscale without relying on expensive equipment. The combination of small size and high order leads to strong interaction with visible light, which induces macroscopic, iridescent structural coloration. To increase the complexity and functionality, it is important to control the organization of such materials in hierarchical structures with high degrees of order spanning multiple length scales. Here, a bottom-up assembly of polystyrene particles in the presence of a silica sol–gel precursor material (tetraethylorthosilicate, TEOS), which creates crack-free inverse opal films with high positional order and uniform crystal alignment along the (110) crystal plane, is combined with top-down microfabrication techniques. Micrometer scale hierarchical superstructures having a highly regular internal nanostructure with precisely controlled crystal orientation and wall profiles are produced. The ability to combine structural order at the nano- and microscale enables the fabrication of materials with complex optical properties resulting from light–matter interactions at different length scales. As an example, a hierarchical diffraction grating, which combines Bragg reflection arising from the nanoscale periodicity of the inverse opal crystal with grating diffraction resulting from a micrometer scale periodicity, is demonstrated.
Phillips KR, Vogel N, Burgess IB, Perry CC, Aizenberg J. Directional Wetting in Anisotropic Inverse Opals. Langmuir [Internet]. 2014;30 (25) :7615-7620. Publisher's VersionAbstract

Porous materials display interesting transport phenomena due to restricted motion of fluids within the nano- to microscale voids. Here, we investigate how liquid wetting in highly ordered inverse opals is affected by anisotropy in pore geometry. We compare samples with different degrees of pore asphericity and find different wetting patterns depending on the pore shape. Highly anisotropic structures are infiltrated more easily than their isotropic counterparts. Further, the wetting of anisotropic inverse opals is directional, with liquids filling from the side more easily. This effect is supported by percolation simulations as well as direct observations of wetting using time-resolved optical microscopy.