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Depletion is one widely used potential to modulate colloidal interaction because it enables the production of a wide variety of crystalline and glassy phases of spherical and shape-tailored colloids. The attractive depletion potential gives rise to qualitatively new behavior. However, depletion-mediated phase behaviors have never been systematically investigated experimentally regarding pair potentials for aqueous suspensions. In this work, we implement three distinct phases of fluid, crystal, and glass by adjusting the concentrations of depletant and salt in the aqueous suspension of polystyrene particles. To define the phase boundary between the fluid and crystal, we calculate pair potential with a superposition of van der Waals, electrostatic, and depletion interactions. Two unknown parameters in the pair potential─the concentration of ionic impurities and the ratio of the molar concentration of depletant to osmolarity─are experimentally determined from sets of reflectance spectra. The interparticle spacing in the crystalline phase is extracted from the peak wavelength originating from Bragg diffraction, which corresponds to the interparticle separation at energy minimum in the pair potential. The boundary between the fluid and crystal is well defined with the depth of the energy well of 3

The scalable synthetic route to colloidal atoms has significantly advanced over the past two decades. Recently, colloidal clusters with DNA-coated cores called "patchy colloidal clusters" have been developed, providing a directional bonding with specific angle of rotation due to the shape complementarity between colloidal clusters. Through a DNA-mediated interlocking process, they are directly assembled into low-coordination colloidal structures, such as cubic diamond lattices. Herein, the significant progress in recent years in the synthesis of patchy colloidal clusters and their assembly in experiments and simulations is reviewed. Furthermore, an outlook is given on the emerging approaches to the patchy colloidal clusters and their potential applications in photonic crystals, metamaterials, topological photonic insulators, and separation membranes.

For over two decades, NaCl nucleation from a supersaturated aqueous solution has been predicted to occur via a two-step nucleation (TSN) mechanism, i.e., two sequential events, the formation of locally dense liquid regions followed by structural ordering. However, the formation of dense liquid regions in the very early stage of TSN has never been experimentally observed. By using a state-of-the-art technique, a combination of electrostatic levitation (ESL) and in situ synchrotron X-ray and Raman scatterings, we find experimental evidence that indicates the formation of dense liquid regions in NaCl bulk solution at an unprecedentedly high level of supersaturation (S = 2.31). As supersaturation increases, evolution of ion clusters leads to chemical ordering, but no topological ordering, which is a precursor for forming the dense disordered regions of ion clusters at the early stage of TSN. Moreover, as the ion clusters proceed to evolve under highly supersaturated conditions, we observe the breakage of the water hydration structure indicating the stability limit of the dense liquid regions, and thus leading to nucleation. The evolution of solute clusters and breakage of hydration in highly supersaturated NaCl bulk solution will provide new insights into the detailed mechanism of TSN for many other aqueous solutions., This work provides evidence for two-step nucleation in highly supersaturated bulk NaCl solution, using electrostatic levitation combined with Raman/X-ray scatterings.

Icosahedral colloidal clusters are a new class of spherical colloidal crystals. This cluster allows for potentially superior optical properties in comparison to conventional onion-like colloidal su...

Equilibrium interfaces were established between body-centered cubic (BCC) crystals and their liquid using charged colloidal particles in an electric bottle. By measuring a time series of interfacial positions and computing the average power spectrum, their interfacial stiffness was determined according to the capillary fluctuation method. For the (100) and the (114) interfaces, the stiffnesses were 0.15 and 0.18 [Formula: see text] (σ: particle diameter), respectively, and were isotropic in the plane of the interface. For comparison, similar charged colloids were used to create an interface between a face-centered cubic (FCC) crystal and its liquid. Its stiffness was significantly larger: 0.26 [Formula: see text]. This result gives experimental support to the explanations offered for the preferential nucleation of BCC over FCC in metallic alloys.

Colloidal assembly in emulsion drops provides fundamental tools for studying optimum particle arrangement under spherical confinement and practical means for producing photonic microparticles. Recent progress has revealed that energetically favored cluster configurations are different from conventional supraballs, which could enhance optical performance. This paper reviews state-of-the-art emulsion-templated colloidal clusters, and particularly focuses on recently reported novel structures such as icosahedral, decahedral, and single-crystalline face-centered cubic (fcc) clusters. We classify the clusters according to the number of component particles as small (N < O(102)), medium (O(102) ≤ N ≤ O(104)), and large (N ≥ O(105)). For each size of clusters, we discuss the detailed structures, mechanisms of cluster formation, and optical properties and potential applications. Finally, we outline current challenges and questions that require further investigation.

We characterize the spatial and temporal coherence properties of hard X-ray pulses from the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL, Pohang, Korea). The measurement of the single-shot speckle contrast, together with the introduction of corrections considering experimental conditions, allows obtaining an intrinsic degree of transverse coherence of 0.85 ± 0.06. In the Self-Amplified Spontaneous Emission regime, the analysis of the intensity distribution of X-ray pulses also provides an estimate for the number of longitudinal modes. For monochromatic and pink (i.e. natural bandwidth provided by the first harmonic of the undulator) beams, we observe that the number of temporal modes is 6.0 ± 0.4 and 90.0 ± 7.2, respectively. Assuming a coherence time of 2.06 fs and 0.14 fs for the monochromatic and pink beam respectively, we estimate an average X-ray pulse duration of 12.6 ± 1.0 fs.

Colloidal particles with a repulsive interparticle potential spontaneously form crystalline lattices, which are used as a motif for photonic materials. It is difficult to predict the crystal arrangement in spherical volume as lattices are incompatible with a spherical surface. Here, the optimum arrangement of charged colloids is experimentally investigated by encapsulating them in double-emulsion drops. Under conditions of strong interparticle repulsion, the colloidal crystal rapidly grows from the surface toward the center of the microcapsule, forming an onion-like arrangement. By contrast, for weak repulsion, crystallites slowly grow and fuse through rearrangement to form a single-crystal phase. Single-crystal structure is energetically favorable even for strong repulsion. Nevertheless, a high energy barrier to colloidal rearrangement kinetically arrests the onion-like structure formed by heterogeneous nucleation. Unlike the isotropic onion-shaped product, the anisotropic single-crystal-containing microcapsules selectively display-at certain orientations but not others-one of the distinct colors from the various crystal planes.

Colloidal crystallization is analogous to the crystallization in bulk atomic systems in various aspects, which has been explored as a model system. However, a real-time probing of the phenomenon still remains challenging. Here, a levitation system for a study of colloidal crystallization is demonstrated. Colloidal particles in a levitated droplet are gradually concentrated by isotropic evaporation of water from the surface of the droplet, resulting in crystallization. The structural change of the colloidal array during crystallization is investigated by simultaneously measuring the volume and reflectance spectra of the droplet. The crystal nucleates from the surface of the droplet at which the volume fraction exceeds the threshold and then the growth proceeds. The crystal growth behavior depends on the initial concentrations of colloidal particles and salts which determine the overall direction of crystal growth and interparticle spacing, respectively. The results show that a levitating bulk droplet has a great potential as a tool for in situ investigation of colloidal crystallization.

Pixelated inverse opals with red, green, and blue colors were prepared by hybridizing convective assembly of colloidal particles and photolithography techniques. The brilliant structural colors, high mechanical stability, and small feature size of the pixels were simultaneously accomplished, thereby providing color reflectors potentially useful for display devices. Moreover, this hybridized method provides a general means to create multi-colored photonic crystals.

Self-assembly of monodisperse colloidal particles into regular lattices has provided relatively simple and economical methods to prepare photonic crystals. The photonic stop band of colloidal crystals appears as opalescent structural colors, which are potentially useful for display devices, colorimetric sensors, and optical filters. However, colloidal crystals have low durability, and an undesired scattering of light makes the structures white and translucent. Moreover, micropatterning of colloidal crystals usually requires complex molding procedures, thereby limiting their practical applications. To overcome such shortcomings, we develop a pragmatic and amenable method to prepare colloidal photonic crystals with high optical transparency and physical rigidity using photocurable colloidal suspensions. The colloidal particles dispersed in a photocurable medium crystallized during capillary force-induced infiltration into a slab, and subsequent photopolymerization of the medium permanently solidifies the st...

We present a simple and reproducible method for the fabrication of three-dimensional (3D) surface-enhanced Raman scattering (SERS) substrates by controlling wettability. A superhydrophilic SU-8 microstructured surface generated using O2 plasma treatment led to the formation of a monolayer of aggregated Ag nanoparticles with nanoscale gaps. The SERS substrate showed a highly sensitive and uniform SERS response.

Advances in microfluidic emulsification have enabled the creation of multiphase emulsion drops, which have emerged as promising templates for producing functional microcapsules. However, most previous micro-encapsulation methods have limitations in terms of capsule stability, functionality, and simplicity of fabrication procedures. Here, we report a simple single-step encapsulation technique that uses an optofluidic platform to efficiently and precisely encapsulate a specific number of emulsion droplets in photocurable shell droplets. In particular, we show, for the first time, that densely confined core droplets within an oily shell droplet rearrange into a unique configuration that minimizes the interfacial energy, as confirmed here from theory. These structures are then consolidated into multi-cored microcapsules with structural and mechanical stability through in situ photopolymerization of the shell in a continuous mode, which are capable of isolating active materials and releasing them in a controlled manner using well-defined nanohole arrays or nanoscopic silver architectures on thin membranes.

In this paper, we demonstrated a microfluidic system for fabricating microspheres with hierarchical surface nanopatterns for molecular detection based on surface-enhanced Raman scattering (SERS). Briefly, a photocurable silica suspension was emulsified into monodisperse droplets using a microfluidic device composed of two coaxial glass capillaries. The silica particles in each droplet protruded through the interface and spontaneously formed a hexagonal array. After polymerization of the droplets, we selectively decorated the exposed areas of the silica particles with silver nanoparticles through electroless deposition. The resulting hierarchically-structured microspheres showed high sensitivity and fast binding kinetics in molecular detection based on SERS, owing to the dense array of hot spots on each microsphere and high mobility of the microspheres, respectively. Notably, the SERS signals from molecules adsorbed on the microspheres could be detected in both the dried and suspension states. In addition, we demonstrated that the SERS-active microspheres can be functionalized into structural colored or magnetoresponsive microspheres for advanced applications.

Advances in microfluidic emulsification have enabled the creation of multiphase emulsion drops, which have emerged as promising templates for producing functional microcapsules. However, most previous micro-encapsulation methods have limitations in terms of capsule stability, functionality, and simplicity of fabrication procedures. Here, we report a simple single-step encapsulation technique that uses an optofluidic platform to efficiently and precisely encapsulate a specific number of emulsion droplets in photocurable shell droplets. In particular, we show, for the first time, that densely confined core droplets within an oily shell droplet rearrange into a unique configuration that minimizes the interfacial energy, as confirmed here from theory. These structures are then consolidated into multi-cored microcapsules with structural and mechanical stability through in situ photopolymerization of the shell in a continuous mode, which are capable of isolating active materials and releasing them in a controlled manner using well-defined nanohole arrays or nanoscopic silver architectures on thin membranes.

We have described a new and promising strategy for the fabrication of composite and porous photonic crystal microparticles that combines the self-assembly of colloidal particles with photolithography techniques. We fabricated silica/SU-8 composite microparticles with photonic bandgaps via four steps: (1) deposition of the silica colloidal crystals on the photoresist, (2) embedding of the colloidal crystals in the photoresist, (3) UV exposure through a photomask and subsequent development, and (4) release of the microparticles from the substrate. Embedding was performed above the glass transition temperature (T(g)) of uncrosslinked SU-8. At such temperatures, capillary forces on the silica particles facilitate the migration of colloidal crystals in the SU-8 matrix. Particle migration ceased when the top colloidal crystal layer was trapped at the interface between air and SU-8. In addition, we also prepared porous microparticles with an inverse opaline structure by dissolving the embedded silica particles from the composite structures. The porous microparticles showed enhanced reflectivity at the bandgap position due to the large refractive index contrast. The bandgap position of the microparticles was controlled by the size of the silica particles, which determined the lattice constant. Bilayered composite and porous microparticles with two distinct photonic bandgaps were also prepared by sequential deposition of colloidal crystals composed of two differently sized silica particles.