An official website of the United States government
DNA-coated colloids can self-assemble into an incredible diversity of crystal structures, but their applications have been limited by poor understanding and control over the crystallization dynamics. To address this challenge, we use microfluidics to quantify the kinetics of DNA-programmed self-assembly along the entire crystallization pathway, from thermally activated nucleation through reaction-limited and diffusion-limited phases of crystal growth. Our detailed measurements of the temperature and concentration dependence of the kinetics at all stages of crystallization provide a stringent test of classical theories of nucleation and growth. After accounting for the finite rolling and sliding rates of micrometer-sized DNA-coated colloids, we show that modified versions of these classical theories predict the absolute nucleation and growth rates with quantitative accuracy. We conclude by applying our model to design and demonstrate protocols for assembling large single crystals with pronounced structural coloration, an essential step in creating next-generation optical metamaterials from colloids.
more »
« less
Macroscopic photonic single crystals via seeded growth of DNA-coated colloids
Abstract Photonic crystals—a class of materials whose optical properties derive from their structure in addition to their composition—can be created by self-assembling particles whose sizes are comparable to the wavelengths of visible light. Proof-of-principle studies have shown that DNA can be used to guide the self-assembly of micrometer-sized colloidal particles into fully programmable crystal structures with photonic properties in the visible spectrum. However, the extremely temperature-sensitive kinetics of micrometer-sized DNA-functionalized particles has frustrated attempts to grow large, monodisperse crystals that are required for photonic metamaterial applications. Here we describe a robust two-step protocol for self-assembling single-domain crystals that contain millions of optical-scale DNA-functionalized particles: Monodisperse crystals are initially assembled in monodisperse droplets made by microfluidics, after which they are grown to macroscopic dimensions via seeded diffusion-limited growth. We demonstrate the generality of our approach by assembling different macroscopic single-domain photonic crystals with metamaterial properties, like structural coloration, that depend on the underlying crystal structure. By circumventing the fundamental kinetic traps intrinsic to crystallization of optical-scale DNA-coated colloids, we eliminate a key barrier to engineering photonic devices from DNA-programmed materials.
more »
« less
- PAR ID:
- 10432066
- Publisher / Repository:
- Nature Publishing Group
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 14
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Starting with Gauss and Kelvin, knots in fields were postulated to behave like particles, but experimentally they were found only as transient features or required complex boundary conditions to exist and could not self-assemble into three-dimensional crystals. We introduce energetically stable, micrometer-sized knots in helical fields of chiral liquid crystals. While spatially localized and freely diffusing in all directions, they resemble colloidal particles and atoms, self-assembling into crystalline lattices with open and closed structures. These knots are robust and topologically distinct from the host medium, though they can be morphed and reconfigured by weak stimuli under conditions such as those in displays. A combination of energy-minimizing numerical modeling and optical imaging uncovers the internal structure and topology of individual helical field knots and the various hierarchical crystalline organizations that they form.more » « less
-
Abstract Photonic crystals are extensively explored to replace inorganic pigments and organic dyes as coloring elements in printing, painting, sensing, and anti‐counterfeiting due to their brilliant structural colors, chemical stability, and environmental friendliness. However, most existing photonic‐crystal‐based pigments can only display monochromatic colors once made, and generating multicolors has to start with designing different building blocks. Here, a novel photonic pigment featuring highly tunable structural colors in the entire visible spectrum, made by the magnetic assembly of monodisperse nanorods into body‐centered‐tetragonal photonic crystals, is reported. Their prominent magnetic and crystal anisotropy makes it efficient to generate multicolors using one photonic pigment by magnetically controlling the crystal orientation. Further, the combination of angle‐dependent diffraction and magnetic orientation control enables the design of rotation‐asymmetric photonic films that display distinct patterns and encrypted information in response to rotation. The efficient multicolor generation through precise orientational control makes this novel photonic pigment promising in developing high‐performance structural‐colored materials and optical devices.more » « less
-
Open colloidal lattices possessing omnidirectional photonic bandgaps in the visible or near-visible regime are attractive optical materials the realization of which has remained elusive. We report the use of an inverse design strategy termed landscape engineering that rationally sculpts the free energy self-assembly landscape using evolutionary algorithms to discover anisotropic patchy colloids capable of spontaneously assembling pyrochlore and cubic diamond lattices possessing complete photonic bandgaps. We validate the designs in computer simulations to demonstrate the defect-free formation of these lattices via a two-stage hierarchical assembly mechanism. Our approach demonstrates a principled strategy for the inverse design of self-assembling colloids for the bottom-up fabrication of desired crystal lattices.more » « less
-
Abstract Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.more » « less
