Colloidal assembly is an attractive means to control material properties via hierarchy of particle composition, size, ordering, and macroscopic form. However, despite well‐established methods for assembling colloidal crystals as films and patterns on substrates, and within microscale confinements such as droplets or microwells, it has not been possible to build freeform colloidal crystal structures. Direct‐write colloidal assembly, a process combining the bottom‐up principle of colloidal self‐assembly with the versatility of direct‐write 3D printing, is introduced in the present study. By this method, centimeter‐scale, free‐standing colloidal structures are built from a variety of materials. A scaling law that governs the rate of assembly is derived; macroscale structural color is tailored via the size and crystalline ordering of polystyrene particles, and several freestanding structures are built from silica and gold particles. Owing to the diversity of colloidal building blocks and the means to control their interactions, direct‐write colloidal assembly could therefore enable novel composites, photonics, electronics, and other materials and devices.
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Abstract -
Abstract Materials made by directed self‐assembly of colloids can exhibit a rich spectrum of optical phenomena, including photonic bandgaps, coherent scattering, collective plasmonic resonance, and wave guiding. The assembly of colloidal particles with spatial selectivity is critical for studying these phenomena and for practical device fabrication. While there are well‐established techniques for patterning colloidal crystals, these often require multiple steps including the fabrication of a physical template for masking, etching, stamping, or directing dewetting. Here, the direct‐writing of colloidal suspensions is presented as a technique for fabrication of iridescent colloidal crystals in arbitrary 2D patterns. Leveraging the principles of convective assembly, the process can be optimized for high writing speeds (≈600 µm s−1) at mild process temperature (30 °C) while maintaining long‐range (cm‐scale) order in the colloidal crystals. The crystals exhibit structural color by grating diffraction, and analysis of diffraction allows particle size, relative grain size, and grain orientation to be deduced. The effect of write trajectory on particle ordering is discussed and insights for developing 3D printing techniques for colloidal crystals via layer‐wise printing and sintering are provided.
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To translate the exceptional properties of colloidal nanoparticles (NPs) to macroscale geometries, assembly techniques must bridge a 106‐fold range of length. Moreover, for successfully attaining a final mechanically robust nanocomposite macroscale material, some of the intrinsic NPs’ properties have to be maintained while minimizing the density of strength‐limiting defects. However, the assembly of nanoscale building blocks into macroscopic dimensions, and their effective macroscale properties, are inherently affected by the precision of the conditions required for assembly and emergent flaws including point defects, dislocations, grain boundaries, and cracks. Herein, a direct‐write self‐assembly technique is used to construct free‐standing, millimeter‐scale columns comprising spherical iron oxide NPs (15 nm diameter) surface functionalized with oleic acid (OA), which self‐assemble into face‐centered cubic (FCC) supercrystals in minutes during the direct‐writing process. The subsequent crosslinking of OA molecules results in nanocomposites with a maximum strength of 110 MPa and elastic modulus up to 58 GPa. These mechanical properties are interpreted according to the flaw size distribution and are as high as newly engineered platelet‐based nanocomposites. The findings indicate a broad potential to create mechanically robust, multifunctional 3D structures by combining additive manufacturing with colloidal assembly.