Gi-Ra Yi

Flexible metal-oxide devices made by room-temperature photochemical activation of sol-gel films

Amorphous metal-oxide semiconductors have emerged as potential replacements for organic and silicon materials in thin-film electronics. The high carrier mobility in the amorphous state, and excellent large-area uniformity, have extended their applications to active-matrix electronics, including displays, sensor arrays and X-ray detectors. Moreover, their solution processability and optical transparency have opened new horizons for low-cost printable and transparent electronics on plastic substrates. But metal-oxide formation by the sol–gel route requires an annealing step at relatively high temperature, which has prevented the incorporation of these materials with the polymer substrates used in high-performance flexible electronics. Here we report a general method for forming high-performance and operationally stable metal-oxide semiconductors at room temperature, by deep-ultraviolet photochemical activation of sol–gel films. Deep-ultraviolet irradiation induces efficient condensation and densification of oxide semiconducting films by photochemical activation at low temperature. This photochemical activation is applicable to numerous metal-oxide semiconductors, and the performance (in terms of transistor mobility and operational stability) of thin-film transistors fabricated by this route compares favourably with that of thin-film transistors based on thermally annealed materials. The field-effect mobilities of the photo-activated metal-oxide semiconductors are as high as 14 and 7 cm2 V−1 s−1 (with an Al2O3 gate insulator) on glass and polymer substrates, respectively; and seven-stage ring oscillators fabricated on polymer substrates operate with an oscillation frequency of more than 340 kHz, corresponding to a propagation delay of less than 210 nanoseconds per stage.

Synthesis and assembly of structured colloidal particles

Synthesis and self-assembly of structured colloids is a nascent field. Recent advances in this area include the development of a variety of practical routes to produce robust photonic band-gap materials, colloidal lithography for nanopatterns, and hierarchically structured porous materials with high surface-to-volume ratios for catalyst supports. To improve their properties, non-conventional suprastructures have been proposed, which could be built up using binary or bimodal mixtures of spherical particles and particles with internal or surface nanostructures. This Feature Article will describe the state-of-the-art in colloidal particles and their assemblies. The paper consists of three main sections categorized by the type of colloid, namely shape-anisotropic particles, chemically patterned particles and internally structured particles. In each section, we will discuss not only synthetic routes to uniform colloids with a range of structures, features and shapes, but also self-organization of these colloids into macrocrystalline structures with varying nanoscopic features and functionalities. Finally, we will outline future perspectives for these colloidal suprastructures.

Characterizing and tracking single colloidal particles with video holographic microscopy

We use digital holographic microscopy and Mie scattering theory to simultaneously characterize and track individual colloidal particles. Each holographic snapshot provides enough information to measure a colloidal spheres radius and refractive index to within 1%, and simultaneously to measure its three-dimensional position with nanometer in-plane precision and 10 nanometer axial resolution.

Shaping colloids for self-assembly

The creation of a new material often starts from the design of its constituent building blocks at a smaller scale. From macromolecules to colloidal architectures, to granular systems, the interactions between basic units of matter can dictate the macroscopic behaviour of the resulting engineered material and even regulate its genesis. Information can be imparted to the building units by altering their physical and chemical properties. In particular, the shape of building blocks has a fundamental role at the colloidal scale, as it can govern the self-organization of particles into hierarchical structures and ultimately into the desired material. Herein we report a simple and general approach to generate an entire zoo of new anisotropic colloids. Our method is based on a controlled deformation of multiphase colloidal particles that can be selectively liquified, polymerized, dissolved and functionalized in bulk. We further demonstrate control over the particle functionalization and coating by realizing patchy and Janus colloids.

Monodisperse micrometer-scale spherical assemblies of polymer particles

Uniform spherical colloidal assemblies of closely packed monodisperse colloidal particles have been prepared by injecting an aqueous suspension of polymer spheres into a surfactant-laden oil phase through a micropipette. The size of these assemblies can be controlled by varying the injection pressure or particle concentration. The Figure shows 6.3 μm diameter assemblies composed of 230 nm particles.

Controlled generation of submicron emulsion droplets via highly stable tip-streaming mode in microfluidic devices

Submicron emulsions could be produced via the tip-streaming process in a flow-focusing microfluidic device. In this article, the stability of the liquid cone and thread for tip-streaming mode could be significantly improved by employing a three-dimensional flow-focusing device, in which the hydraulic resistance was adjusted by modulating the channel heights in the flow focusing area, orifice, downstream and dispersed phase inlet channel. The pressure range for tip-streaming mode was enlarged significantly compared with two-dimensional flow-focusing devices. Therefore, monodisperse emulsions were produced under this tip-streaming mode for as long as 48 hours. Furthermore, we could control the size of emulsion drops by changing the pressure ratio in three-dimensional flow-focusing devices while the liquid cone was easily retracted during the adjustment of pressure ratio in two-dimensional flow-focusing devices. Furthermore, using the uniform submicron emulsion droplets as confining templates, polyethylene glycol (PEG) particles were produced with a narrow size distribution at the sub-micrometre scale. In addition, magnetic nanoparticles were added to the emulsion for magnetic PEG particles, which can respond to magnetic field and would be biocompatible.

Size-Controlled Nanoparticle-Guided Assembly of Block Copolymers for Convex Lens-Shaped Particles

The tuning of interfacial properties at selective and desired locations on the particles is of great importance to create the novel structured particles by breaking the symmetry of their surface property. Herein, a dramatic transition of both the external shape and internal morphology of the particles of polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) was induced by precise positioning of size-controlled Au nanoparticle surfactants (Au NPs). The size-dependent assembly of the Au NPs was localized preferentially at the interface between the P4VP domain at the particle surface and the surrounding water, which generated a balanced interfacial interaction between two different PS/P4VP domains of the BCP particles and water, producing unique convex lens-shaped BCP particles. In addition, the neutralized interfacial interaction, in combination with the directionality of the solvent-induced ordering of the BCP domains from the interface of the particle/water, generated defect-free, vertically ordered porous channels within the particles. The mechanism for the formation of these novel nanostructures was investigated systemically by varying the size and the volume fraction of the Au NPs. Furthermore, these convex lens-shaped particles with highly ordered channels can be used as a microlens, in which the light can be concentrated toward the focal point with enhanced near-field signals. And, these particles can possess additional optical properties such as unique distribution of light scattering as a result of the well-ordered Au cylinders that filled into the channels, which hold great promise for use in optical, biological-sensing, and imaging applications.

Ultrasmooth, highly spherical monocrystalline gold particles for precision plasmonics

Ultrasmooth, highly spherical monocrystalline gold particles were prepared by a cyclic process of slow growth followed by slow chemical etching, which selectively removes edges and vertices. The etching process effectively makes the surface tension isotropic, so that spheres are favored under quasi-static conditions. It is scalable up to particle sizes of 200 nm or more. The resulting spherical crystals display uniform scattering spectra and consistent optical coupling at small separations, even showing Fano-like resonances in small clusters. The high monodispersity of the particles we demonstrate should facilitate the self-assembly of nanoparticle clusters with uniform optical resonances, which could in turn be used to fabricate optical metafluids. Narrow size distributions are required to control not only the spectral features but also the morphology and yield of clusters in certain assembly schemes.

Gold-Decorated Block Copolymer Microspheres with Controlled Surface Nanostructures

Gold-decorated block copolymer microspheres (BCP-microspheres) displaying various surface morphologies were prepared by the infiltration of Au precursors into polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) microspheres. The microspheres were fabricated by emulsifying the PS-b-P4VP polymers in chloroform into a surfactant solution in water, followed by the evaporation of chloroform. The selective swelling of the P4VP domains in the microspheres by the Au precursor under acidic conditions resulted in the formation of Au-decorated BCP-microspheres with various surface nanostructures. As evidenced by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) measurements, dotted surface patterns were formed when microspheres smaller than 800 nm were synthesized, whereas fingerprint-like surface patterns were observed with microspheres larger than 800 nm. Au nanoparticles (NPs) were located inside P4VP domains near the surfaces of the prepared microspheres, as confirmed by TEM. The optical properties of the BCP-microspheres were characterized using UV-vis absorption spectroscopy and fluorescence lifetime measurements. A maximum absorption peak was observed at approximately 580 nm, indicating that Au NPs are densely packed into P4VP domains on the microspheres. Our approach for creating Au-NP-hybrid BCP-microspheres can be extended to other NP systems such as iron-oxide or platinum NPs. These precursors can also be selectively incorporated into P4VP domains and induce the formation of hybrid BCP-microspheres with controlled surface nanostructures.

Photocurable Pickering Emulsion for Colloidal Particles with Structural Complexity

We prepared polymeric microparticles with coordinated patches using oil-in-water emulsion droplets which were stabilized by adsorbed colloidal polystyrene (PS) latex particles. The oil phase was photocurable ethoxylated trimethylolpropane triacrylate (ETPTA), and the particle-armored oil droplets were solidified by UV irradiation within a few seconds to produce ETPTA-PS composite microparticles without disturbing the structures. Large armored emulsion drops became raspberry-like particles, while small emulsion drops with a few anchored particles were transformed into colloidal clusters with well-coordinated patches. For high-molecular-weight PS particles with low chemical affinity to the ETPTA monomer, the morphology of the patchy particle was determined by the volume of the emulsion drop and the contact angle of the emulsion interface on the PS particle surface. Meanwhile, for low-molecular-weight PS particles with high affinity, the ETPTA monomers were likely to swell the adsorbed PS particles, and distinctive morphologies were induced during the shrinkage of emulsion drops and the phase separation of ETPTA from the swollen PS particles. In addition, colloidal particles with large open windows were produced by dissolving the PS particles from the patchy particles. We observed photoluminescent emission from the patchy particles in which dye molecules were dispersed in the ETPTA phase. Finally, we used Surface Evolver simulation to predict equilibrium structures of patchy particles and estimate surface energies which are essential to understand the underlying physics.