Self-assembly

Phillips KR, England GT, Sunny S, Shirman E, Shirman T, Vogel N, Aizenberg J. A colloidoscope of colloid-based porous materials and their uses. Chem. Soc. Rev. 2016;45 (2) :281-322. Full TextAbstract
Nature evolved a variety of hierarchical structures that produce sophisticated functions. Inspired by these natural materials, colloidal self-assembly provides a convenient way to produce structures from simple building blocks with a variety of complex functions beyond those found in nature. In particular, colloid-based porous materials (CBPM) can be made from a wide variety of materials. The internal structure of CBPM also has several key attributes, namely porosity on a sub-micrometer length scale, interconnectivity of these pores, and a controllable degree of order. The combination of structure and composition allow CBPM to attain properties important for modern applications such as photonic inks, colorimetric sensors, self-cleaning surfaces, water purification systems, or batteries. This review summarizes recent developments in the field of CBPM, including principles for their design, fabrication, and applications, with a particular focus on structural features and materials' properties that enable these applications. We begin with a short introduction to the wide variety of patterns that can be generated by colloidal self-assembly and templating processes. We then discuss different applications of such structures, focusing on optics, wetting, sensing, catalysis, and electrodes. Different fields of applications require different properties, yet the modularity of the assembly process of CBPM provides a high degree of tunability and tailorability in composition and structure. We examine the significance of properties such as structure, composition, and degree of order on the materials' functions and use, as well as trends in and future directions for the development of CBPM.
Phillips KR, Vogel N, Hu Y, Kolle M, Perry CC, Aizenberg J. Tunable Anisotropy in Inverse Opals and Emerging Optical Properties. Chem. Mater. 2014;26 (4) :1622-1628. Publisher's VersionAbstract

Using self-assembly, nanoscale materials can be fabricated from the bottom up. Opals and inverse opals are examples of self-assembled nanomaterials made from crystallizing colloidal particles. As self-assembly requires a high level of control, it is challenging to use building blocks with anisotropic geometry to form complex opals, which limits the possible structures. Typically, spherical colloids are employed as building blocks, leading to symmetric, isotropic superstructures. However, a significantly richer palette of directionally dependent properties are expected if less symmetric, anisotropic structures can be created, especially originating from the assembly of regular, spherical particles. Here we show a simple method for introducing anisotropy into inverse opals by subjecting them to a post-assembly thermal treatment that results in directional shrinkage of the silica matrix caused by condensation of partially hydrated sol−gel silica structures. In this way, we can tailor the shape of the pores, and the anisotropy of the final inverse opal preserves the order and uniformity of the self-assembled structure. Further, we prevent the need to synthesize complex oval-shaped particles and crystallize them into such target geometries. Detailed X-ray photoelectron spectroscopy and infrared spectroscopy studies clearly identify increasing degrees of sol−gel condensation in confinement as a mechanism for the structure change. A computer simulation of structure changes resulting from the condensation-induced shrinkage further confirmed this mechanism. As an example of property changes induced by the introduction of anisotropy, we characterized the optical spectra of the anisotropic inverse opals and found that the optical properties can be controlled in a precise way using calcination temperature.

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. 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.
Kaplan CN, Wu N, Mandre S, Aizenberg J, Mahadevan L. Dynamics of evaporative colloidal patterning. Physics of Fluids. 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.

Vasquez Y, Kolle M, Mishchenko L, Hatton BD, Aizenberg J. Three-Phase Co-Assembly: In-situ Incorporation of Nanoparticles into Tunable, Highly-Ordered, Porous Silica FIlms. ACS Photonics. 2014;1 (1) :53-60. Full TextAbstract

We present a reproducible, one-pot colloidal co-assembly approach that results in large-scale, highly ordered porous silica films with embedded, uniformly distributed, accessible gold nanoparticles. The unique coloration of these inverse opal films combines iridescence with plasmonic effects. The coupled optical properties are easily tunable either by changing the concentration of added nanoparticles to the solution before assembly or by localized growth of the embedded Au nanoparticles upon exposure to tetrachloroauric acid solution, after colloidal template removal. The presence of the selectively absorbing particles furthermore enhances the hue and saturation of the inverse opals’ color by suppressing incoherent diffuse scattering. The composition and optical properties of these films are demonstrated to be locally tunable using selective functionalization of the doped opals.

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