Programmable Assembly of Hybrid Nanoclusters.

Hybrid nanoparticle clusters (often metallic) are interesting plasmonic materials with tunable resonances and a near-field electromagnetic enhancement at interparticle junctions. Therefore, in recent years, we have witnessed a surge in both the interest in these materials and the efforts to obtain them. However, a versatile fabrication of hybrid nanoclusters, that is, combining more than one material, still remains an open challenge. Current lithographical or self-assembly methods are limited to the preparation of hybrid clusters with up to two different materials and typically to the fabrication of hybrid dimers. Here, we provide a novel strategy to deposit and align not only hybrid dimers but also hybrid nanoclusters possessing more complex shapes and compositions. Our strategy is based on the downscaling of sequential capillarity-assisted particle assembly over topographical templates. As a proof of concept, we demonstrate dimers, linear trimers, and 2D nanoclusters with programmable compositions from a range of metallic nanoparticles. Our process does not rely on any specific chemistry and can be extended to a large variety of particles and shapes. The template also simultaneously aligns the hybrid (often anisotropic) nanoclusters, which could facilitate device integration, for example, for optical readout after transfer to other substrates by a printing step. We envisage that this new fabrication route will enable the assembly and positioning of complex hybrid nanoclusters of different functional nanoparticles to study coupling effects not only locally but also at larger scales for new nanoscale optical devices.

Capillary assembly as a tool for the heterogeneous integration of micro- and nanoscale objects.

During the past decade, capillary assembly in topographical templates has evolved into an efficient method for the heterogeneous integration of micro- and nano-scale objects on a variety of surfaces. This assembly route has been applied to a large spectrum of materials of micrometer to nanometer dimensions, supplied in the form of aqueous colloidal suspensions. Using systems produced via bulk synthesis affords a huge flexibility in the choice of materials, holding promise for the realization of novel superior devices in the fields of optics, electronics and health, if they can be integrated into surface structures in a fast, simple, and reliable way. In this review, the working principles of capillary assembly and its fundamental process parameters are first presented and discussed. We then examine the latest developments in template design and tool optimization to perform capillary assembly in more robust and efficient ways. This is followed by a focus on the broad range of functional materials that have been realized using capillary assembly, from single components to large-scale heterogeneous multi-component assemblies. We then review current applications of capillary assembly, especially in optics, electronics, and in biomaterials. We conclude with a short summary and an outlook for future developments.

Enhanced Second-Harmonic Generation from Sequential Capillarity-Assisted Particle Assembly of Hybrid Nanodimers.

We show enhanced second-harmonic generation (SHG) from a hybrid metal-dielectric nanodimer consisting of an inorganic perovskite nanoparticle of barium titanate (BaTiO3) coupled to a metallic gold (Au) nanoparticle. BaTiO3-Au nanodimers of 100 nm/80 nm sizes are fabricated by sequential capillarity-assisted particle assembly. The BaTiO3 nanoparticle has a noncentrosymmetric crystalline structure and generates bulk SHG. We use the localized surface plasmon resonance of the gold nanoparticle to enhance the SHG from the BaTiO3 nanoparticle. We experimentally measure the nonlinear signal from assembled nanodimers and demonstrate an up to 15-fold enhancement compared to a single BaTiO3 nanoparticle. We further perform numerical simulations of the linear and SHG spectra of the BaTiO3-Au nanodimer and show that the gold nanoparticle acts as a nanoantenna at the SHG wavelength.

Hybrid colloidal microswimmers through sequential capillary assembly.

Active colloids, also known as artificial microswimmers, are self-propelled micro- and nanoparticles that convert uniform sources of fuel (e.g. chemical) or uniform external driving fields (e.g. magnetic or electric) into directed motion by virtue of asymmetry in their shape or composition. These materials are currently attracting enormous scientific attention as models for out-of-equilibrium systems and with the promise to be used as micro- and nanoscale devices. However, current fabrication of active colloids is limited in the choice of available materials, geometries, and modes of motion. Here, we use sequential capillarity-assisted particle assembly (sCAPA) to link microspheres of different materials into hybrid clusters of prescribed shapes ("colloidal molecules") that can actively translate, circulate and rotate powered by asymmetric electro-hydrodynamic flows. We characterize the active motion of the clusters and highlight the range of parameters (composition and shape) that can be used to tune their trajectories. Further engineering provides active colloids that switch motion under external triggers or perform simple pick-up and transport tasks. By linking their design, realization and characterization, our findings enable and inspire both physicists and engineers to create customized active colloids to explore novel fundamental phenomena in active matter and to investigate materials and propulsion schemes that are compatible with future applications.

Hybrid Colloids Produced by Sequential Capillarity-assisted Particle Assembly: A New Path for Complex Microparticles.

Colloidal particles have long been under the spotlight of a very diverse research community, given their ubiquitous presence in a broad class of materials and processes, and their pivotal role as model systems. More recently, intense efforts have been devoted to the development of micro- and nanoparticles combining multiple materials in objects with a controlled architecture, hence introducing multiple functionalities and a prescribed symmetry for interactions. These particles are often called hybrid colloids or colloidal molecules, given the analogy with classical molecules presenting well defined structures and chemical compositions. Here, we review the recent progress made in our group to fabricate a broad library of hybrid colloids exploiting a novel assembly route, which uses capillary forces at the moving edge of an evaporating droplet for the sequential composition of colloidal clusters, whose geometry and chemistry can be independently programmed.

Cascaded assembly of complex multiparticle patterns.

A method for the cascaded capillary assembly of different particle populations in a single assembly cycle is presented. The method addresses the increasing need for fast and simple fabrication of multicomponent arrays from colloidal micro- and nanoscale building blocks for constructing nanoelectronic, optical, and sensing devices. It is based on the use of a microfluidic device from which two independent capillary bridges extend. The menisci of the capillary bridges are pulled over a template with trapping sites that receive the colloidal particles. We describe the parameters for simultaneous, high-yield assembly from both menisci and demonstrate the applicability of the process by means of the size-selective assembly of particles of different diameters and also by the fabrication of two-component particle clusters with defined shape and composition. This approach allows the fabrication of multifunctional particle clusters having different functionalities at predetermined positions.

Programmable colloidal molecules from sequential capillarity-assisted particle assembly.

The assembly of artificial nanostructured and microstructured materials which display structures and functionalities that mimic nature's complexity requires building blocks with specific and directional interactions, analogous to those displayed at the molecular level. Despite remarkable progress in synthesizing "patchy" particles encoding anisotropic interactions, most current methods are restricted to integrating up to two compositional patches on a single "molecule" and to objects with simple shapes. Currently, decoupling functionality and shape to achieve full compositional and geometrical programmability remains an elusive task. We use sequential capillarity-assisted particle assembly which uniquely fulfills the demands described above. This is a new method based on simple, yet essential, adaptations to the well-known capillary assembly of particles over topographical templates. Tuning the depth of the assembly sites (traps) and the surface tension of moving droplets of colloidal suspensions enables controlled stepwise filling of traps to "synthesize" colloidal molecules. After deposition and mechanical linkage, the colloidal molecules can be dispersed in a solvent. The template's shape solely controls the molecule's geometry, whereas the filling sequence independently determines its composition. No specific surface chemistry is required, and multifunctional molecules with organic and inorganic moieties can be fabricated. We demonstrate the "synthesis" of a library of structures, ranging from dumbbells and triangles to units resembling bar codes, block copolymers, surfactants, and three-dimensional chiral objects. The full programmability of our approach opens up new directions not only for assembling and studying complex materials with single-particle-level control but also for fabricating new microscale devices for sensing, patterning, and delivery applications.

Insights into mechanisms of capillary assembly.

Capillary assembly in a topographical template is a powerful and flexible method for fabricating complex and programmable particle assemblies. To date, very little attention has been paid to the effects that the trap geometry--in particular the trap depth--has on the outcome of the assembly process. In this paper, we provide insights into the mechanisms behind this directed assembly method by systematically studying the impact of the trap depth and the surface tension of the suspension. Using confocal microscopy, we investigate the assembly process at the single-particle level and use these observations to formulate a simple mechanical model that offers guidelines for the successful assembly of single or multiple particles in a trap. In particular, single particles are assembled for shallow traps and moderate surface tensions, opening up the possibility to fabricate multifunctional particle dimers in two consecutive assembly steps.