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Metal halide perovskite nanocrystals (PeNCs) with a controlled quantum size effect have received intense interest for potential applications in optoelectronics and photonics. Here, we present a simple and innovative strategy to precisely tune the photoluminescence color of PeNCs by simply printing perovskite precursor solutions on cellulose papers. Depending on the volume of the printed precursor solutions, the PeNCs are autonomously grown into three discrete sizes, and their relative size population is controlled; accordingly, not only the number of multiple PL peaks but also their relative intensities can be precisely tuned. This autonomous size control is obtained through the efflorescence, which is advection of salt ions toward the surface of a porous medium during solvent evaporation and also through the confined crystal growth in the hierarchical structure of cellulose fibers. The infiltrated PeNCs are environmentally stable against moisture (for 3 months in air at 70% relative humidity) and strong light exposure by hydrophobic surface treatment. This study also demonstrates invisible encryption and highly secured unclonable anticounterfeiting patterns on deformable cellulose substrates and banknotes.

Metal thin films with a specific orientation play vital roles in electronics, catalysts, and epitaxial templates. Although oriented metal films have been produced in the recent years, ultrathin oriented metal films (

With emerging interest in foldable and stretchable displays, the need to develop transparent deformable electrode and interconnection is increasing. Even though metal films have been standard electrodes in conventional electronic devices due to their high conductivity and well-established process, they have never been used for transparent deformable electrodes. We present highly conductive transparent deformable Au film electrodes and use them to fabricate a foldable perovskite light-emitting diode (PeLED) and a biaxially stretchable alternating current electroluminescence (ACEL) display. We exhibit the formation of an ultrathin (6 nm) continuous Au film on an anisotropic conductive ultrathin film (ACUF) of amorphous carbon. The ultrathin Au film was first formed on an ACUF-coated Si wafer (4 in. scale) through metal evaporation and transferred to the polymer substrates by a simple and effective water-assisted delamination process. Then, a hybrid electrode (ACUF/ACUF/Au) was produced as the transparent deformable electrode. Complicated interconnections could be created by metal deposition through a mask. The electrical conductance of the hybrid electrode was not affected by the crack formation in the Au film during electrode folding, crumpling, and stretching. We reveal the reason why the hybrid electrode can maintain such excellent electrical stability under deformation.

A triboelectric nanogenerator (TENG) is an attractive alternative source of electric power generation; however, its direct use is difficult due to the spike-like alternating current (AC) output. Th...

Transparent flexible transistor array requests large-area fabrication, high integration, high manufacturing throughput, inexpensive process, uniformity in transistor performance, and reproducibility. This study suggests a facile and reliable approach to meet the requirements. We use the Al-coated polymer nanofiber patterns obtained by electrohydrodynamic (EHD) printing as a photomask. We use the lithography and deposition to produce highly aligned nanolines (NLs) of metals, insulators, and semiconductors on large substrates. With these NLs, we demonstrate a highly integrated NL field-effect transistor (NL-FET) array (10

Colloidal particles with a spherical shape and diameters in the range of 0.01−1 μm have been a subject of extensive research, with applications in areas such as photonics, electronics, catalysis, drug delivery, and medicine. For most of these applications, it is of critical importance to achieve monodispersity for the size while expanding the diversity in terms of structure and composition. The uniformity in size allows one to establish rigorous correlations between this parameter and the physicochemical properties of the colloidal particles while ensuring experimental repeatability and measurement accuracy. On the other hand, the diversity in structure and composition offers additional handles for tailoring the properties. By switching from the conventional plain, solid structure to a core-shell, hollow, porous, or Janus structure, it offers immediate advantages and creates new opportunities, especially in the context of self-assembly, encapsulation, and controlled release. As for composition, monodispersed colloidal spheres were traditionally limited to amorphous materials such as polystyrene and silica. For metals and semiconducting materials, which are more valuable to applications in photonics, electronics, and catalysis, they tend to crystallize and thus grow anisotropically into non-spherical shapes, especially when their sizes pass 0.1 μm. Taken together, it is no wonder why chemical synthesis of monodispersed colloidal spheres has been a constant theme of research in areas such as colloidal science, materials chemistry, materials science, and soft matter. In this account, we summarize our efforts over the past two decades in developing solution-phase methods for the facile synthesis of colloidal spheres that are uniform in size, together with a broad range of compositions (including metals and semiconductors) and structures (e.g., solid, core-shell, hollow, porous, and Janus, among others). We start with the synthesis of monodispersed colloidal spheres made of semiconductors, metals with low melting points, and precious metals. Through chemical reactions, these colloidal spheres can be transformed into core-shell or hollow structures with new compositions and properties. Next, we discuss the synthesis of colloidal spheres with a Janus structure while taking a pseudo-spherical shape. Specifically, metal-polymer hybrid particles comprised of one metal nanoparticle partially embedded in the surface of a polymer sphere can be produced through precipitation polymerization in the presence of metal seed. With these Janus particles serving as templates, other types of Janus structures such as hollow spheres with a single hole in the surface can be obtained via site-selected deposition. Alternatively, such hollow spheres can be fabricated through a physical transformation process that involves swelling of polymer spheres, followed by freeze-drying. All these synthesis and transformation processes are solution-based, offering flexibility and potential for large-scale production. At the end, we highlight some of the applications enabled by these colloidal spheres, including fabrication of photonic devices, encapsulation, and controlled release for nanomedicine.

As industrial needs for healthcare sensors, electronic skin, and flexible/stretchable displays increase, interest in stretchable materials is increasing as well. In recent years, the studies on stretchable materials have spread to various pivot components, such as electrodes, circuits, substrates, semiconductors, dielectric layers, membranes, and active nanocomposite films. The block copolymer (BC) elastomers have been playing considerable role in the development of stretchable materials. Since BCs are soft elastomers based on physical cross-links, they show differences in physical properties from normal elastomers formed with chemical cross-linking. BC elastomers does not require additional chemical cross-linking procedure, so they can be easily processed after dissolved in various solvents. Their viscoelasticity and thermoplasticity enable the BCs to become moldable and sticky. Although their unique physical properties may serve as disadvantages in some cases, they have been actively applied to create various stretchable electronic materials and their uses are expected to be enlarged more than ever. In this Account, we summarize recent successful applications of BCs for the stretchable electronic devices and discuss the possibility of further uses and the challenges to be addressed for practical uses. Studies on BC-based stretchable materials have focused initially on the fabrication process of stretchable conductors; mixing conductive fillers physically with BCs, infiltrating BCs in a conductive filler layer, and converting metal precursors into metal nanoparticles inside BCs. When conductive fillers with high aspect ratios, such as nanowires or nanosheets are used, the fillers can be infiltrated by the BCs after deposited. Since the contacts between the fillers are maintained during the infiltration process, even thin composite films possess high conductivity and stretchability. The metal precursor solution printing is suggested as a promising approach because it is compatible with traditional printing techniques without clogging the nozzles and allows high filler loading efficiency. When using a BC as a substrate, it is advisable to use a BC/PDMS double layer because of viscoelastic and thermoplastic properties of BCs. If BC/PDMS double layer is used with much thicker PDMS layer instead of viscoelastic BC alone, the double layer substrate can show a perfect elastomeric behavior, and the advantages of the BC substrate are preserved. Additionally, the use of conventional manufacturing techniques is important for commercialization of the stretchable devices. BC substrates having preformed microfibril network on their surfaces facilitate the fabrication of high-resolution circuitry by directly depositing metals through a mask on the substrate. Recent successes of fabricating stretchable organic transistors were obtained based on in situ phase separation of polymer semiconductors to form nanofibril bundles on the surface of a BC substrate. They have led to the achievement of high resolution transistor array printed in large area. BCs are expected to expand their applicability, including stretchable batteries, since they make it feasible to fabricate various hybrid nanocomposites, pore size-controlled membranes, and microstructured surfaces. However, it is necessary to secure long-term stability under heat, solvent, and UV; in addition, there is a need for the synthesis of functional BCs for use in stretchable implanted biomedical devices.

Flexible tactile sensors have been intensively studied for healthcare and electronic skin devices. Currently, a sensing material, electrode, and substrate are manufactured as one set by depositing the sensing material on the electrode. For this reason, when another electrode or substrate is used in the sensor or when different sensor characteristics are required, a new sensing material must be developed and the fabrication conditions should be changed. This study proposes a novel method of manufacturing a pressure sensing material like a cartridge film. The cartridge film is made by filling the holes of a stencil film (one MP in each hole) with conductive microparticles (MPs). Using the cartridge film, the sensing material can be cut-and-pasted on electrodes and transferred to other electrodes for reuse. This study analyzes the electrical responses of the sensors made of the cartridge film on the basis of the Hertzian contact theory, and also correlates the sensing performance of the sensors with the cond...

The controlled synthesis of large-area, atomically thin molybdenum and tungsten ditelluride (MoTe2 and WTe2) crystals is crucial for their emerging applications based on the attractive electronic properties. However, the solution phase synthesis of high-quality and large-area MoTe2 or WTe2 ultrathin films have not been achieved yet. In this study, we synthesized for the first time, large-area atomically thin MoTe2 and WTe2 films in solution phase, through rapid crystal formation directly on a conducting substrate. For the synthesis, we developed a new Te precursor. The crystal growth involves an in situ chemical transformation from Te nanoparticles into MoTe2 or WTe2 thin films. The synthesis enables precise control of the number of atomic layers over a large area, from a monolayer to multilayers. Micropatterned MoTe2 thin films are also readily synthesized in situ using the same process. The photodetector made of 3-layer semiconducting MoTe2 thin films exhibits high photoresponsivity (Rλ) over a broad sp...

We investigated, for the first time, the conditions where a thermoplastic conductive composite can exhibit completely reversible stretchability at high elongational strains (ε = 1.8). We studied a composite of Au nanosheets and a polystyrene-block-polybutadiene-block-polystyrene block copolymer as an example. The composite had an outstandingly low sheet resistance (0.45 Ω/sq). We found that when a thin thermoplastic composite film is placed on a relatively thicker chemically cross-linked elastomer film, it can follow the reversible elastic behavior of the bottom elastomer. Such elasticity comes from the restoration of the block copolymer microstructure. The strong adhesion of the thermoplastic polymer to the metallic fillers is advantageous in the fabrication of mechanically robust, highly conductive, stretchable electrodes. The chemical stability of the Au composite was used to fabricate high luminescence, stretchable electrochemiluminescence displays with a conventional top-bottom electrode setup and with a horizontal electrode setup.

Many studies have reported the synthesis of two-dimensional (2D) nanoplates and nanosheets of the layer-structured metal chalcogenides but also have reported various structures far from the 2D shape. In multicomponent compounds, the elemental concentrations keep changing during the reaction; hence, the reactions are considered to be nonstoichiometric from the nucleation and may include continuous changes in the structure and composition. The different shapes of the metal chalcogenides with the layered structure are attributed to the nonstoichiometric reactions. However, it has not been studied if such nonstoichiometric reactions eventually produce 2D nanoplates, and the mechanism involved in the transformation has not been understood. This study investigates a two-step chemical reaction as an extreme nonstoichiometric nucleation and growth. It reveals that the layer-structured metal chalcogenides (M2X3, M = Sb and Bi, X = Se and Te) with the R3m space group can be obtained by transforming premade pure ch...

A novel method (i.e., continuous magnetic cell separation in a microfluidic channel) is demonstrated to be capable of inducing multifractionation of mixed cell suspensions into multiple outlet fractions. Here, multicomponent cell separation is performed with three different distinguishable magnetic nanoclusters (MnFe2O4, Fe3O4, and CoFe2O4), which are tagged on A431 cells. Because of their mass magnetizations, which can be ideally altered by doping with magnetic atom compositions (Mn, Fe, and Co), the trajectories of cells with each magnetic nanocluster in a flow are shown to be distinct when dragged under the same external magnetic field; the rest of the magnetic characteristics of the nanoclusters are identically fixed. This proof of concept study, which utilizes the magnetization-controlled nanoclusters (NCs), suggests that precise and effective multifractionation is achievable with high-throughput and systematic accuracy for dynamic cell separation.

The fabrication of deformable devices has been explored by interconnecting nonstretchable unit devices with stretchable conductors or by developing stretchable unit devices consisting of all stretchable device components such as electrodes, active channels, and dielectric layers. Most researches have followed the first approach so far, and the researches based on the second approach are at the very beginning stage. This paper discusses the perspectives of the second approach, specifically focusing on the polymer semiconductor channel layers, that is expected to facilitate high density device integration in addition to large area devices including polymer solar cells and light-emitting diodes. Three different routes are suggested as separate sections according to the principles imparting stretchability to polymer semiconductor layers: structural configurations of rigid semiconductors, two-dimensional network structure of semiconductors on elastomer substrates, and ductility enhancement of semiconductor fil...

Morphological control over polythiophenes has been widely studied; however the impacts of regioregularity (RR) and molecular weight (MW) on their structural development have not been investigated systematically. This study examined a representative polythiophene, poly(3-hexylthiophene) (P3HT), to reveal that small differences in the RR can produce a large difference in the growth of nanofibrils. Low-RR P3HTs generated neat long nanofibrils (LNFs), whereas high-RR P3HTs formed short nanofibrils (SNFs). This study identified a critical RR (96-98%) depending on their MW, below which P3HT grew into LNFs and above which P3HT grew into SNFs. This study also found that the mixing ratio between high-RR P3HT and a low-RR P3HT in the solution phase is strongly correlated with the relative populations of SNF and LNF in the coated film. This study suggested that mixing high-RR and low-RR polymers may be a good strategy to optimize the electrical properties of polythiophenes for target applications. As an example, a mixture of high-RR (75%) P3HT and low-RR P3HT (25%) improved considerably the power conversion efficiency of bulk heterojunction polymer solar cells compared with the values obtained from the pure high-RR P3HT and the pure low-RR P3HT.

Highly stretchable conductors are essential components in deformable electronics. Owing to their high stretchability and conductivity, liquid metals have attracted significant attention for use as circuits and interconnections. However, their poor wettability to stretchable metal electrodes prevents the formation of stable electrical connections. This study examined two approaches for creating a stable interface between a liquid metal (EGaIn) and stretchable metal electrodes via: (i) the use of honeycomb-structured stretchable metal electrodes and (ii) the addition of a conducting polymer interlayer. The line width of the honeycomb had a significant influence on the formation of a stable interface. The liquid metal formed a stable film layer on honeycomb metal electrodes, which have line widths of less than 50 μm. CoatingPSS with a nonionic surfactant lowered the interfacial energy of EGaIn with flat stretchable metal surfaces; hence EGaIn was coated uniformly on the stretchable metal surfaces. Strain sensors were fabricated as a demonstrative example of an application that utilizes the stable interface.

The ability to assemble nanoscale functional building blocks is a useful and modular way for scientists to design valuable materials with specific physical and chemical properties. Chemists expect multicomponent, heterostructured nanocrystals to show unique electrical, thermal, and optical properties not seen in homogeneous, single-phase nanocrystals. Although researchers have made remarkable advances in heterogeneous nucleation and growth, design of synthetic conditions for obtaining nanocrystals with a target composition and shape is still a big challenge. There are several outstanding issues that chemists need to address before they can successfully carry out the design-based synthesis of multicomponent nanocrystals. For instance, small changes in the reaction parameters, such as the precursor, solvent, surfactant, reducing agent, and the reaction temperature, often result in changes in the structure and chemical composition of the final product. Although scientists do not fully understand the mechanisms underlying the nucleation and growth processes involved in the synthesis of these multicomponent nanocrystals, recent progress in understanding of the thermodynamic and kinetic factors have improved our control over their final structure and chemical composition. In this Account, we summarize our recent advances in understanding of the nucleation and growth mechanisms involved in the solution-based synthesis of multicomponent nanocrystals. We also discuss the various challenges encountered in their synthesis, emphasizing what still needs special consideration. We first discuss the three different nucleation paths from a thermodynamics perspective: amorphous nucleation, crystalline nucleation, and two-step nucleation. Amorphous nucleation and two-step nucleation involve the generation of nonstoichiometric nuclei. We initiate this process mainly by introducing an imbalance in the concentrations of the reduced elements. When the nonstoichiometric nuclei grow, we can add secondary elements to the growing nonstoichiometric nuclei. This leads to either the physical deposition or atomic mixture formation through the diffusion and rearrangement of constituents. The processes of mixture formation and the physical deposition of the secondary constituent element also compete and determine the shape and chemical composition of the final product. If the free energy change by mixture formation is positive (ΔGAB ≥ 0), physical deposition takes place predominantly, and the spreading coefficient (S) determines the structure of the nanocrystals. However, when mixture formation is highly spontaneous (ΔGAB < -ξ), the chemical composition of the final product is usually stoichiometric, and its shape then depends on the size of the primary nanocrystals. When the mixture formation and physical deposition are in competition (-ξ ≤ ΔGAB < 0), as commonly seen for many nanoalloy systems, both the chemical composition and the structure are determined by the size of the primary nanocrystals as well as the degree of mixture formation at the interface of the constituent components. Finally, we discuss the challenges and caveats that one needs to take into account when synthesizing multicomponent nanocrystals.

We demonstrate here that an improvement in the green density leads to a great enhancement in the photovoltaic performance of CuInSe2 (CISe) solar cells fabricated with Cu-In nanoparticle precursor films via colloidal solution deposition. Cold-isostatic pressing (CIP) increases the precursor film density by ca. 20%, which results in an appreciable improvement in the microstructural features of the sintered CISe film in terms of a lower porosity, a more uniform surface morphology, and a thinner MoSe2 layer. The low-band-gap (1.0 eV) CISe solar cells with the CIP-treated films exhibit greatly enhanced open-circuit voltage (V(OC), typically from 0.265 to 0.413 V) and fill factor (FF, typically from 0.34 to 0.55), compared to the control devices. As a consequence, an almost 3-fold increase in the average efficiency, from 3.0 to 8.2% (with the highest value of 9.02%), is realized. Diode analysis reveals that the enhanced V(OC) and FF are essentially attributed to the reduced reverse saturation current density and diode ideality factor. This is associated with suppressed recombination, likely due to the reduction in recombination sites at grain/air surfaces, intergranular interfaces, and defective CISe/CdS junctions. From the temperature dependences of V(OC), it is revealed that CIP-treated devices suffer less from interface recombination.

This paper describes a novel approach for composite nanofiber mats and its application to fabricate a strain sensor. Electrospun poly(4-vinylpyridine) (P4VP) nanofiber mats are micropatterned by a lithographic approach that includes selective oxidation of the nanofibers and removal of unreacted fibers. The P4VP/HAuCl4 complex is converted to P4VP/Au composites by chemical reduction. We investigate the electrical resistivity of the composite mats according to the number of complexation-and-reduction cycles, the thickness of the fiber mats, and the annealing temperatures which control the percolation of the Au nanoparticles in the fiber mats. Nozzle printing of a polymeric solution on the patterned nanofiber mats simply produces an array of strain-sensitive and strain-invariant units. The patterns demonstrate high strain-sensing performance without any mechanical and electrical failure over 200 bending cycles in the strain range of e < 0.17.

A low-cost, nonvacuum fabrication route for CuInSe2 and CuInS2 thin films is presented. To produce these films, binder-free colloidal precursors were prepared using Cu–In intermetallic nanoparticles that were synthesized via a chemical reduction method. The Cu–In alloy precursor films were transformed to CuInSe2 and CuInS2 by reactive annealing in chalcogen-containing atmospheres at atmospheric pressure. The as-synthesized nanoparticles and the annealed films were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectrometry, electron probe X-ray microanalysis, Raman spectroscopy, and Auger electron spectroscopy depth profile measurements to elucidate the phase evolution pathway and the densification mechanism of the Cu–In–Se–S system. Solar cell devices made with CuInSe2 and CuInS2 absorbing layers exhibited power conversion efficiencies of 3.92% and 2.28%, respectively. A comparison of the devices suggested that the microstructur...

Applying conventional printing technologies to fabricate large-area flexible bulk heterojunction (BHJ) solar cells is of great interest. Achieving this task requires (i) large tolerance of the maximum photoconversion efficiency (PCE) to the film thickness, (ii) fast hole transport in both the thickness and lateral directions of the BHJ layer, and (iii) improved stability against bending and heat. This paper demonstrates that a P3HT:PCBM BHJ layer made of long P3HT nanofibrils of almost 100% crystallinity can be an excellent approach to achieve large-area printed solar cells. We applied a cool-and-heat (C&H) process with a P3HT/PCBM m-xylene solution to generate P3HT:PCBM nanofibril composite films. We found that the hole transport of the nanofibril composite was 2.6 times faster in the thickness direction and 6.5 times more conductive in the in-plane direction compared with conventionally annealed composites. The fast hole transport in the thickness direction led to negligible dependence of the PCE on the...

In spite of the recent successes in transistors and solar cells utilizing poly(3-hexylthiophene) (P3HT) nanofibrils, systematic analysis on the growth kinetics has not been reported due to the lack of analytical tools. This study proposed a simple spectroscopic method to obtain the crystallinity of P3HT in solutions. On the basis of the analytical approach, we found that the crystallinity hysteresis upon temperature is a simple function of the solubility parameter difference (Δδ) between the P3HT and the solvents. When Δδ ≥ 0.7, a cooling (−20 °C)-and-heating (25 °C) process allowed the preparation of solutions including 1D crystal seeds dispersed in the solution. Simple coating of the seeded solutions completed the growth of the seeds into long nanofibrils at the early stage of the coating and thereby achieved almost 100% crystallinity in the resulting films without any postannealing process. The existence of PCBM for bulk-heterojunction (BHJ) solar cells did not affect the nucleation and growth of the n...

It is often observed that polymer patterns fabricated by capillary force lithography (CFL) are not identical, position-dependent even in one sample. The drawback has not been successfully explained so far. This paper reveals that the position-dependent pattern is mainly caused by the volume expansion and contraction of the elastomer stamp during heating and cooling in the CFL process. The stamp expands on a polymer liquid on heating, accumulating the polymer at one side-wall of each pattern of the stamp. And the stamp shrinks back to the initial position, accumulating the polymer at the opposite wall of the stamp pattern. For crystalline polymers, the morphology was mainly determined by the annealing temperature, that is, the degree of expansion. The position-dependence of the morphology was enhanced as the annealing temperature was increased. For amorphous polymers, the morphology was sensitive to cooling rate. Fast cooling led to a frozen morphology generated at the hot annealing temperature, while slow cooling produced an opposite morphology from the one at the annealing. The experimental results were theoretically explained by analyzing thermal expansion of the stamp and the shear stress exerted in the polymer layer. In the conclusion, we added our suggestions to avoid the nonuniformity in the polymer pattern by CFL process.

A facile and quick approach to prepare self-assembled monolayers of water-dispersible particles on the water surface is presented. Particle suspensions in alcohols were dropped on a water reservoir to form long-range ordered monolayers of various particles, including spherical solid particles, soft hydrogel particles, metal nanoparticles, quantum dots, nanowires, single-wall carbon nanotubes (SWCNTs), nanoplates, and nanosheets. A systematic study was conducted on the variables affecting the monolayer assembly: the solubility parameter of spreading solvents, particle concentration, zeta potential of the particles in the suspension, surface tension of the water phase, hardness of the particles, and addition of a salt in the suspension. This method requires no hydrophobic surface treatment of the particles, which is useful to exploit these monolayer films without changing the native properties of the particles. The study highlights a quick 2D colloidal assembly without cracks in the wafer scale as well as transparent conductive thin films made of SWCNTs and graphenes.

This study demonstrates solution-processed epitaxial growth of Te on Se(x)Te(y) nanorods and the generation of periodic defects in the core. We investigated Se(x)Te(y)@Te core-shell nanorods with a diameter of 40-50 nm and a length of 600-700 nm. In spite of a large lattice mismatch between the Se(x)Te(y) core and the Te shell, the soft character of the core and the shell at a high reaction temperature allowed epitaxial growth of Te on the Se(x)Te(y) nanorods. During the cooling process to room temperature (below the glass transition temperatures), the lattice mismatch between the core and the shell led to homogeneous stress along the epitaxial interface so that periodic defects were generated in the core.

This paper demonstrates that simple cross-stamping in capillary force lithography (CFL) enables the fabrication of periodic dots, rings, and line patterns of the metal/polymer composites. The key to the success was the compatibility of polymer/inorganic precursor composite liquids on substrates. As a model study, the composites consisting of poly(ethylene oxide) (PEO) and the gold precursor (HAuCl4) were investigated. The contact angle of the composite liquid on the Si substrate significantly increased when the fractional composition of the precursor was over a critical value, while the contact angle on poly(dimethylsiloxane) (PDMS) molds decreased. The reduced wettability on the substrate resulted in isolated dot patterns upon cross-stamping on the line patterns fabricated by CFL. The shape, size, and number of the dots could be controlled by adjusting the thickness of the composite films. Small coupled dots were obtained from dual-line patterns and large single dots were obtained from single-line patter...

We have studied the chemical transformations in ultrathin chalcogenide nanowires with an aim to understand the parameters that control the morphology and crystal structure of the product. Ultrathin Te nanowires were transformed into Ag2Te nanowires with preservation of the single crystallinity. The Ag2Te nanowires were then converted into CdTe, ZnTe, and PbTe using cation-exchange reactions, and the CdTe nanowires were further transformed into PtTe2 nanotubes. On the basis of the solubility products of the ionic solids, the crystal structures of the involved solids, the reaction kinetics, and the reaction conditions for transformations, we were able to reach the following conclusions: (i) The solubility products of ionic solids can be used as a rough criterion to predict if the transformation is thermodynamically favorable or not. (ii) The morphological preservation of reactant nanowires is more sensitive to the change in length rather than the total volume in addition to the lattice matching between the reactant and product nanowires. (iii) The crystal structure resulting from a transformation should be determined by the free energy of formation and the stability of the products. (iv) The transformation involving small volume change or topotactic lattice matching is considered homogeneous along the entire length of the nanowires, preserving both the single crystallinity and the morphology of the reactant nanowires.

Long ultrathin Cd(OH)(2) nanowires have been selectively grown on silica colloids in a basic aqueous condition. The Cd(OH)(2) nanowires could be detached from the surface of the silica colloids by simply applying ultrasonication and then transformed into isolated CdSe nanocrystal chains. When the transformation into CdSe was conducted without detaching the Cd(OH)(2) nanowires, nanoporous CdSe shells composed of wire-like nanocrystal chains were produced. The good solubility of the Cd(OH)(2) nanowires in both hydrophilic and hydrophobic solvents facilitated the formation of composites with quantum dots, magnetic particles, organic molecules, and polymers. Embedding premade quantum dots possessed broad light absorption range and enhanced photoluminescence. Large amount of superparamagnetic particles endowed a fast magnetic response in addition to the fluorescence. Composites of organic/nanocrystal chains were readily fabricated by employing the electrostatic attraction between the positively charged Cd(OH)(2) nanowires and negatively charged polymers or small molecules.

High-performance organic field-effect transistors (OFETs) based on polyelectrolyte gate dielectric and electrospun poly(3-hexylthiophene) (P3HT) nanofibers were fabricated on a flexible polymer substrate. The use of UV-crosslinked hydrogel including ionic liquids for the insulating layer enabled fast and large-area fabrication of transistor arrays. The P3HT nanofibers were directly deposited on the methacrylated polymer substrate. During UV irradiation through a patterned mask, the methacrylate groups formed covalent bonds with the patterned polyelectrolyte dielectric layer, which provides mechanical stability to the devices. The OFETs operate at voltages of less than 2 V. The average field-effect mobility and on/off ratio were approximately 2 cm(2)/(Vs) and 10(5), respectively.

Physical separation of Ag(2)Se colloids and trigonal (t) Se nanowires transformed from amorphous (a) Se@Ag(2)Se core-shell spherical colloids and from t-Se@Ag(2)Se core-shell nanowires was conducted above the softening temperature ( approximately 132 degrees C) of Ag(2)Se. The Ag(2)Se shells in a-Se@Ag(2)Se core-shell colloids were first collapsed and then transformed into isolated solid spheres as the a-Se cores were dissolved in solvent and transformed into separate t-Se nanowires. In t-Se@Ag(2)Se core-shell nanowires, the soft Ag(2)Se shells dewetted on the t-Se nanowires and transformed into small droplets. While the formation of the spherical Ag(2)Se was not affected by the presence of surfactants, the structure of t-Se was highly dependent on the chemical structure of the polymeric surfactants.

The microdomain orientation in thin films of cylinder- and lamella-forming diblock copolymers, polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA), was investigated as a function of the film thickness and the composition of random copolymers composed of styrene (S) and methyl methacrylate (MMA), denoted as P(S-r-MMA), that were anchored to the substrate. Using scanning force microscopy (SFM) and grazing incidence small-angle X-ray scattering (GISAXS), the dependence of the microdomain orientation on film thickness around lattice period (or d-spacing, L0), where the microdomain orientations normal to the film surface could be achieved, showed that the optimal condition for the balanced interfacial interactions (the so-called neutrality in random copolymer) was 0.64 of PS mole fraction (XPS) for the cylindrical microdomain having narrow compositional range of P(S-r-MMA) from 0.52 to 0.72 of XPS, whereas for the lamella microdomain it was observed at XPS = 0.55 ranging extensively from 0.48 to 0.78.

This paper describes the generation of Pt nanoparticles inside hollow silica colloids. Solvent etching of a-Se core in a-Se@Pt@silica double-shelled colloids transformed the thin Pt layer into a number of Pt nanoparticles, decorating the interior surface of hollow silica colloids. The release rate of a-Se was directly related to the formation of Pt nanoparticles. Fast dissolution of the core in solvents such as carbon disulfide (CS2) and hydrazine (N2H4) produced Pt nanoparticles with diameters less than 15 nm, while slow release of a-Se in alcohols or in a mixture of CS2 and water did not make any change in the Pt thin layer. At elevated temperatures (65 °C) in alcohols, the nanoparticles were aggregated and rearranged into large nanoparticles. The nanoparticles obtained in these processes were characterized single crystallites with HR-TEM analysis and electron diffraction patterns.

Microscale fish bowls, hollow particles with engineered holes in their surfaces, were prepared using two different methods. In the first method, commercial latex beads suspended in water were swollen with a good solvent of the polymer, followed by freezing with liquid nitrogen and evaporation of the solvent below 0 degrees C. While one big hole was generated when the amount of solvent used for the swelling was relatively low, small holes could be produced in the outer surface of each bowl by increasing the degree of swelling. The porosity and pore structure show a similar dependence on the degree of swelling for both amorphous and semicrystalline polymers even though they are supposed to exhibit different phase behaviors during the freezing and solvent evaporation processes. In the second method, a polymer emulsion in water was prepared and then frozen with liquid nitrogen, followed by solvent evaporation below 0 degrees C. The porosity and pore structure could be controlled by adjusting the concentration of the polymer solution used to prepare the emulsion. As for encapsulation, the bowl-shaped particles could be transformed back into solid beads via thermal annealing at a temperature near the glass transition temperature of the polymer or by adding a good solvent of the polymer to the colloidal suspension. In a proof-of-concept experiment, microscale fish bowls were fabricated from poly(caprolactone), quickly loaded with a fluorescent dye, and sealed through thermal annealing. The encapsulated dye could then be slowly released in a phosphate buffered saline, suggesting their potential use as a new class of microscale capsules for drug delivery.

The effect of various end-functional groups on the phase behavior of polystyrene-block-poly(n-butyl methacrylate) copolymer (PS-b-PnBMA) was investigated by using small-angle X-ray scattering, conventional and 3-D transmission electron microscopy, rheology, and Fourier-transformed infrared spectroscopy. A PS-b-PnBMA with maleic anhydride (SBM66-MAH) exhibited an unexpected thermoreversible transition occurring at higher temperature than its disorder-to-order transition temperature. The transition was very fast and induced a large increase in shear modulus. However, the transition at higher temperature was not observed in other PS-b-PnBMAs with carboxylic acid, diester, and hydrogen end groups.

Thin films of mixtures of asymmetric poly(styrene-block-methyl methacrylate) (PS-b-PMMA) diblock copolymers and PMMA homopolymers with cylindrical PMMA microdomains oriented normal to the substrate surface were used to couple optical modes in the Kretschmann configuration, and their optical properties were investigated by optical waveguide spectroscopy (OWS). The nanopore formation in the block copolymer (BCP) waveguide layer via selective solvent swelling and subsequent reannealing was monitored in terms of shifts in the coupling mode angles. The sequential swelling/reannealing of the initial mixture film resulted in a number of discrete or partially interconnected pores instead of cylindrical pores with a high aspect ratio. The simultaneous processes occurring inside and on top of the BCP waveguide layer were discerned independently with high selectivity for p- and s-polarization.

Monodispersed spherical core-shell colloids of Se@Ag(2)Se have been exploited as a chemical template to synthesize Se@CdSe core-shell particles using a cation-exchange reaction. A small amount of tributylphosphine could facilitate the replacement of Ag(+) by Cd(2+) in methanol at 50 degrees C to complete the conversion within 150 min. The orthorhombic structure of beta-Ag(2)Se changed to a well-defined wurtzite lattice for CdSe. The CdSe shells could be converted back to beta-Ag(2)Se by reacting with AgNO(3) in methanol at room temperature. Because of the uniformity in size and high refractive index associated with the Se@CdSe core-shell colloids, they could serve as a new class of building blocks to fabricate photonic crystals with wide and strong stop bands.

An electric field was applied to reactive bilayer thin films consisting of poly(methyl methacrylate-ran-glycidyl methacrylate) (PMMA−GMA) and polystyrene (PS) with various amounts of monocarboxylic acid end-functionalized PS (PS-mCOOH). The fast growing wavelength (λmax) of the interfacial fluctuation under an electric field decreased sharply and approached a steady value with increasing amounts of PS-mCOOH. This is because of the decrease in interfacial tension (γ) between PMMA−GMA and PS resulting from the formation of PMMA-g-PS copolymers in-situ from the reaction between two functional groups of GMA and mCOOH. The reduction of γ with increasing amount of PS-mCOOH was verified from a reduction in the dispersed domain size. For a reactive bilayer where Y-shaped graft copolymers were formed, the pillars with flattened top surface were observed even when they did not touch the upper electrode. This result is in contrast to that seen for nonreactive bilayer or even other reactive bilayer where diblock copo...

The phase behavior of polystyrene-block-poly(n-pentyl methacrylate) copolymers [PS−PnPMA] having various block length ratios was investigated by rheology, transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). All of the PS−PnPMA exhibited two transitions: the lower disorder-to-order transition (LDOT) and upper order-to-disorder transition (UODT) occurring at a lower and higher temperature, respectively. Thus, PS−PnPMA is characterized by a closed-loop type of phase behavior. As the volume fraction of PS in PS−PnPMA was decreased from 0.5 to 0.23, the microdomains observed between the LDOT and UODT changed from lamellae (LAM) to hexagonally packed cylinders (HEX) and finally to body-centered-cubic spheres (BCC), similar to other block copolymers exhibiting only an order-to-disorder transition. The rheological properties depended strongly on the type of microdomains within the closed-loop. The storage and loss moduli (G‘ and G‘ ‘) within the closed loop are the highest for a PS−P...

Mixtures of polystyrene-block-poly(methyl methacrylate) (PS−PMMA) having PMMA cylindrical microdomains with homopolymers of PMMA and poly(ethylene oxide) (PEO) were used to study the effect of the interaction between homopolymers confined to the cylindrical microdomains and the PS matrix on the microdomain spacing of the mixtures. The microdomains in all thin films are oriented perpendicular to the film surface. It was found that the miscibility between PMMA homopolymer and PMMA block in thin film was enhanced compared with that in bulk at a given molecular weight of PMMA homopolymer. Also, the PMMA homopolymer chains in thin films were more localized to the center of PMMA microdomains than in the bulk, which results in a larger increase of the lattice spacing (D) in the former. D increased rapidly at low volume fractions of PMMA homopolymer, but it approached a saturated value as the content of PMMA increased. The increase of D with increasing molecular weight of PMMA homopolymer was saturated at a certa...

The phase behavior of deuterated polystyrene-block-poly(n-pentyl methacrylate) copolymers (dPS−PnPMA) was investigated by using small-angle X-ray (SAXS) and neutron (SANS) scatterings and rheology. This block copolymer exhibited a closed-loop type of phase behavior as did hydrogenated PS−PnPMA copolymers. The closed loop consists of two transitions: lower disorder-to-order transition (LDOT) and upper order-to-disorder transition (UODT) occurring at a lower and higher temperature, respectively. The segmental interaction parameter (χ) between dPS and PnPMA blocks at various temperatures was obtained by fitting the incompressible random phase approximation theory to SANS results using a low molecular weight of dPS−PnPMA exhibiting a disordered homogeneous state over the entire temperature range. We found that at higher temperatures χ increased initially with increasing temperature (T), achieved a maximum, and then decreased. Such behavior is in keeping with polymer blends or block copolymers that would exhi...

The kinetics and mechanism of morphological transition from nonequilibrium lamella to cylinder microdomain in a polystyrene-block-poly(ethylene-co-but-1-ene)-block-polystyrene (SEBS) triblock copolymer were studied by using time-resolved synchrotron small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and rheology. The sample cast from toluene solution formed a nonequilibrium morphology of the alternating lamellae (LAM) of polystyrene (PS) and poly(ethylene-co-but-1-ene) (PEB) blocks because toluene is a good solvent for PS chains but a poor solvent for PEB chains. LAM of PS and PEB blocks was transformed into the hexagonally close packing (HEX) of PS cylinders in PEB matrix when the as-cast sample was annealed above 140 °C, which is above the glass transition temperature of the PS block. From the time-resolved SAXS and TEM, the coexistence of the LAM and HEX microdomains was clearly confirmed during the entire process of the order-to-order transition (OOT) from LAM to HEX, and the...

The temporal change of complex viscosity (η*) of two plates consisting of an end-functional monocarboxylated polystyrene (PS−mCOOH) and poly(methyl methacrylates) (PMMA) with various amounts of pol...

This paper describes the growth of t-Se nanowires on the srufaces of a-Se@Ag2Se core−shell colloids. The number and dimension of the t-Se nanowires were controled by adjusting the release of Se through the Ag2Se shells.

We have successfully incorporated iron oxide nanoparticles into monodispersed amorphous selenium (a-Se) colloids by regulating the reaction temperature during the synthesis of a-Se. The surfaces of these a-Se colloids could be coated with conformal and smooth shells made of Pt and SiO2. The Se cores could then be removed by etching with hydrazine. The spherical morphology and superparamagnetism were maintained in all these synthetic steps. The presence of Pt and SiO2 on the outer surfaces of these colloidal particles allows one to control their surface functionalities through the formation of alkanethiolate and siloxane monolayers, respectively.