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The fast and efficient synthesis of nanoparticles on flexible and lightweight substrates is increasingly critical for various medical and wearable applications. However, conventional high temperature (high-T) processes for nanoparticle synthesis are intrinsically incompatible with temperature-sensitive substrates, including textiles and paper ( i.e. low-T substrates). In this work, we report a non-contact, ‘fly-through’ method to synthesize nanoparticles on low-T substrates by rapid radiative heating under short timescales. As a demonstration, textile substrates loaded with platinum (Pt) salt precursor are rapidly heated and quenched as they move across a 2000 K heating source at a continuous production speed of 0.5 cm s −1 . The rapid radiative heating method induces the thermal decomposition of various precursor salts and nanoparticle formation, while the short duration ensures negligible change to the respective low-T substrate along with greatly improved production efficiency. The reported method can be generally applied to the synthesis of metal nanoparticles ( e.g. gold and ruthenium) on various low-T substrates ( e.g. paper). The non-contact and continuous ‘fly-through’ synthesis offers a robust and efficient way to synthesize supported nanoparticles on flexible and lightweight substrates. It is also promising for ultrafast and roll-to-roll manufacturing to enable viable applications.
Anchoring nanoscale building blocks, regardless of their shape, into specific arrangements on surfaces presents a significant challenge for the fabrication of next-generation chip-based nanophotonic devices. Current methods to prepare nanocrystal arrays lack the precision, generalizability, and postsynthetic robustness required for the fabrication of device-quality, nanocrystal-based metamaterials [Q. Y. Lin et al. Nano Lett. 15, 4699–4703 (2015); V. Flauraud et al., Nat. Nanotechnol. 12, 73–80 (2017)]. To address this challenge, we have developed a synthetic strategy to precisely arrange any anisotropic colloidal nanoparticle onto a substrate using a shallow-template-assisted, DNA-mediated assembly approach. We show that anisotropic nanoparticles of virtually any shape can be anchored onto surfaces in any desired arrangement, with precise positional and orientational control. Importantly, the technique allows nanoparticles to be patterned over a large surface area, with interparticle distances as small as 4 nm, providing the opportunity to exploit light–matter interactions in an unprecedented manner. As a proof-of-concept, we have synthesized a nanocrystal-based, dynamically tunable metasurface (an anomalous reflector), demonstrating the potential of this nanoparticle-based metamaterial synthesis platform.
Controlled aggregation of nanoparticles into superlattices is a grand challenge in material science, where ligand based self‐assembly is the dominant route. Here, the self‐assembly of gold nanoparticles (AuNPs) that are crosslinked by water soluble oligo‐(ethylene glycol)‐dithiol (oEG‐dithiol) is reported and their 3D structure by small angle X‐ray scattering is determined. Surprisingly, a narrow region is found in the parameter space of dithiol linker‐length and nanoparticle size for which the crosslinked networks form short‐ranged FCC crystals. Using geometrical considerations and numerical simulations, the stability of the formed lattices is evaluated as a function of dithiol length and the number of connected nearest‐neighbors, and a phase diagram of superlattice formation is provided. Identifying the narrow parameter space that allows crystallization facilitates focused exploration of linker chemical composition and medium conditions such as thermal annealing, pH, and added solutes that may lead to superior and more robust crystals.
Dissipative Self‐Assembly of Anisotropic Nanoparticle Chains with Combined Electrodynamic and Electrostatic Interactions
Dissipative self‐assembly of colloidal nanoparticles offers the prospect of creating reconfigurable artificial materials and systems, yet the phenomenon only occurs far from thermodynamic equilibrium. Therefore, it is usually difficult to predict and control. Here, a dissipative colloidal solution system, where anisotropic chains with different interparticle separations in two perpendicular directions transiently arise among largely disordered silver nanoparticles illuminated by a laser beam, is reported. The optical field creates a nonequilibrium dissipative state, where a disorder‐to‐order transition occurs driven by anisotropic electrodynamic interactions coupled with electrostatic interactions. Investigation of the temporal dynamics and spatial arrangements of the nanoparticle system shows that the optical binding strength and entropy of the system are two crucial parameters for the formation of the anisotropic chains and responsible for adaptive behaviors, such as self‐replication of dimer units. Formation of anisotropic nanoparticle chains is also observed among colloidal nanoparticles made from other metal (e.g., Au), polymer (e.g., polystyrene), ceramic (e.g., CeO2), and hybrid materials (e.g., SiO2@Au core–shell), suggesting that light‐driven self‐organization will provide a wide range of opportunities to discover new dissipative structures under thermal fluctuations and build novel anisotropic materials with nanoscale order.
Crystallization is a universal phenomenon underpinning many industrial and natural processes and is fundamental to chemistry and materials science. However, microscopic crystallization pathways of nanoparticle superlattices have been seldom studied mainly owing to the difficulty of real-time observation of individual self-assembling nanoparticles in solution. Here, using in situ electron microscopy, we directly image the full self-assembly pathway from dispersed nanoparticles into ordered superlattices in nonaqueous solution. We show that electron-beam irradiation controls nanoparticle mobility, and the solvent composition largely dictates interparticle interactions and assembly behaviors. We uncover a multistep crystallization pathway consisting of four distinct stages through multi-order-parameter analysis and visualize the formation, migration, and annihilation of multiple types of defects in nanoparticle superlattices. These findings open the door for achieving independent control over imaging conditions and nanoparticle assembly conditions and will enable further study of the microscopic kinetics of assembly and phase transition in nanocolloidal systems.