Sub‐Nanometer Level Size Tuning of a Monodisperse Nanoparticle Array Via Block Copolymer Lithography

The fabrication and catalytic application of a size‐tunable monodisperse nanoparticle array enabled by block copolymer lithography is demonstrated. Highly uniform vertical cylinder nanodomains are achieved in poly(styrene‐block‐4‐vinylpyridine) (PS‐b‐P4VP) diblock copolymer thin‐films by solvent annealing. The prominent diffusion of the anionic metal complexes into the protonated P4VP cylinder nanodomains occurs through specific electrostatic interactions in a weakly acidic aqueous solution. This well‐defined diffusion with nanoscale confinement enables preparation of the laterally ordered monodisperse nanoparticle array with sub‐nanometer level precise size tuning. The controlled growth of monodisperse nanoparticle arrays is proven by their catalytic use for vertical carbon nanotube (CNT) growth via plasma enhanced chemical vapor deposition (PECVD). Since the size of the catalyst particles is the decisive parameter for the diameters and wall‐numbers of CNTs, the highly selective growth of double‐walled or triple‐walled CNTs could be accomplished using monodisperse nanoparticle arrays.     

Large‐scale Synthesis of Urchin‐like Mesoporous TiO2 Hollow Spheres by Targeted Etching and Their Photoelectrochemical Properties

A versatile targeted etching strategy is developed for the large‐scale synthesis of urchin‐like mesoporous TiO₂ hollow spheres (UMTHS) with tunable particle size. Its key feature is the use of a low‐temperature hydrothermal reaction of surface‐fluorinated, amorphous, hydrous TiO₂ solid spheres (AHTSS) under the protection of a polyvinylpyrrolidone (PVP) coating. With the confinement of PVP and water penetration, the highly porous AHTSS are selectively etched and hollowed by fluoride without destroying their spherical morphology. Meanwhile TiO₂ hydrates are gradually crystallized and their growth is preferentially along anatase (101) planes, reconstructing an urchin‐like shell consisting of numerous radially arranged single‐crystal anatase nanothorns. Complex hollow structures, such as core–shell and yolk–shell structures, can also be easily synthesized via additional protection of the interior by pre‐filling AHTSS with polyethylene glycol (PEG). The hollowing transformation is elucidated by the synergetic effect of etching, PVP coating, low hydrothermal reaction temperature, and the unique microstructure of AHTSS. The synthesized UMTHS with a large surface area of up to 128.6 m² g^‐1 show excellent light‐harvesting properties and present superior performances in photocatalytic removal of gaseous nitric oxide (NO) and photoelectrochemical solar energy conversion as photoanodes for dye‐sensitized mesoscopic solar cells.     

Highly Fluorescent and Color‐Tunable Exciplex Emission from Poly(N‐vinylcarbazole) Film Containing Nanostructured Supramolecular Acceptors

Highly fluorescent excited‐state charge‐transfer complexes (exciplexes) formed at the interfacial region between a polymeric donor matrix, here, poly(N‐vinylcarbazole), and embedded nanostructured acceptors are characterized for their photophysical properties. Exciplex‐to‐exciton emission switching is observed after solvent vapor annealing (SVA) due to the size evolution of the nanostructures beyond the exciton diffusion length. Color‐tunable exiplex emission (sky blue, green, and orange) is demonstrated for three different nanostructured acceptors with the same HOMO–LUMO gap (i.e., the same blue excitonic emission) but with different electron affinity. White‐emitting poly(N‐vinylcarbazole) film is also fabricated, simply by incorporating mixed supramolecular acceptors, which provide independent exciplex emissions. This study presents important insights into the excited‐state intermolecular interaction at the well‐defined nanoscale interface and suggests an efficient way to obtain multicolored exciplex emissions.     

A Review of Three‐Dimensional Resistive Switching Cross‐Bar Array Memories from the Integration and Materials Property Points of View

Issues in the circuitry, integration, and material properties of the two‐dimensional (2D) and three‐dimensional (3D) crossbar array (CBA)‐type resistance switching memories are described. Two important quantitative guidelines for the memory integration are provided with respect to the required numbers of signal wires and sneak current paths. The advantage of 3D CBAs over 2D CBAs (i.e., the decrease in effect memory cell size) can be exploited only under certain limited conditions due to the increased area and layout complexity of the periphery circuits. The sneak current problem can be mitigated by the adoption of different voltage application schemes and various selection devices. These have critical correlations, however, and depend on the involved types of resistance switching memory. The problem is quantitatively dealt with using the generalized equation for the overall resistance of the parasitic current paths. Atomic layer deposition is discussed in detail as the most feasible fabrication process of 3D CBAs because it can provide the device with the necessary conformality and atomic‐level accuracy in thickness control. Other subsidiary issues related to the line resistance, maximum available current, and fabrication technologies are also reviewed. Finally, a summary and outlook on various other applications of 3D CBAs are provided.     

3‐Level Envelope Delta‐Sigma Modulation RF Signal Generator for High‐Efficiency Transmitters

This paper presents a 0.13 μm CMOS 3‐level envelope delta‐sigma modulation (EDSM) RF signal generator, which synthesizes a 2.6 GHz‐centered fully symmetrical 3‐level EDSM signal for high‐efficiency power amplifier architectures. It consists of an I‐Q phase modulator, a Class B wideband buffer, an up‐conversion mixer, a D2S, and a Class AB wideband drive amplifier. To preserve fast phase transition in the 3‐state envelope level, the wideband buffer has an RLC load and the driver amplifier uses a second‐order BPF as its load to provide enough bandwidth. To achieve an accurate 3‐state envelope level in the up‐mixer output, the LO bias level is optimized. The I‐Q phase modulator adopts a modified quadrature passive mixer topology and mitigates the I‐Q crosstalk problem using a 50% duty cycle in LO clocks. The fabricated chip provides an average output power of –1.5 dBm and an error vector magnitude (EVM) of 3.89% for 3GPP LTE 64 QAM input signals with a channel bandwidth of 10/20 MHz, as well as consuming 60 mW for both channels from a 1.2 V/2.5 V supply voltage.     

Biomimetic Chitin–Silk Hybrids: An Optically Transparent Structural Platform for Wearable Devices and Advanced Electronics

The cuticles of insects and marine crustaceans are fascinating models for man‐made advanced functional composites. The excellent mechanical properties of these biological structures rest on the exquisite self‐assembly of natural ingredients, such as biominerals, polysaccharides, and proteins. Among them, the two commonly found building blocks in the model biocomposites are chitin nanofibers and silk‐like proteins with β‐sheet structure. Despite being wholly organic, the chitinous protein complex plays a key role for the biocomposites by contributing to the overall mechanical robustness and structural integrity. Moreover, the chitinous protein complex alone without biominerals is optically transparent (e.g., dragonfly wings), thereby making it a brilliant model material system for engineering applications where optical transparency is essentially required. Here, inspired by the chitinous protein complex of arthropods cuticles, an optically transparent biomimetic composite that hybridizes chitin nanofibers and silk fibroin (β‐sheet) is introduced, and its potential as a biocompatible structural platform for emerging wearable devices (e.g., smart contact lenses) and advanced displays (e.g., transparent plastic cover window) is demonstrated.     

Skin-like Omnidirectional Stretchable Platform with Negative Poisson's Ratio for Wearable Strain–Pressure Simultaneous Sensor

Conventional elastomeric polymers used as substrates for wearable platforms have large positive Poisson's ratios (≈0.5) that cause a deformation mismatch with human skin that is multidirectionally elongated under bending of joints. This causes practical problems in elastomer-based wearable devices, such as delamination and detachment, leading to poorly reliable functionality. To overcome this issue, auxetic-structured mechanical reinforcement with glass fibers is applied to the elastomeric film, resulting in a negative Poisson's ratio (NPR), which is a skin-like stretchable substrate (SLSS). Several parameters for determining the materials and geometrical dimensions of the auxetic-structured reinforcing fillers are considered to maximize the NPR. Based on numerical simulation and digital image correlation analysis, the deformation tendencies and strain distribution of the SLSS are investigated and compared with those of the pristine elastomeric substrate. Owing to the strain-localization characteristics, an independent strain-pressure sensing system is fabricated using SLSS with a Ag-based elastomeric ink and a carbon nanotube-based force-sensitive resistor. Finally, it is demonstrated that the SLSS-based sensor platform can be applied as a wearable device to monitor the physical burden on the wrist in real time.     

Double S-Shaped Polarization – Voltage Curve and Negative Capacitance from Al2O3-Hf0.5Zr0.5O2-Al2O3 Triple-Layer Structure

The negative capacitance (NC) effect, recently discovered in a fluorite-based ferroelectric thin film, has attracted great attention as a rescue to overcome the scaling limitations of the conventional memory and logic devices of highly integrated circuits. The NC effect manifesting an S-shaped polarization–voltage (P–V) curve is initially interpreted by a 1-dimensional Landau Ginzburg Devonshire (LGD) model. However, a series of recent studies have found that this effect can also be explained by the inhomogeneous stray field energy (ISE) model. In this study, by extending the ISE model in the ferroelectric (FE)-dielectric (DE) layered structure, an analytical model that considers the influence of the interfacial screening charge distribution is presented. This model showed that the NC effect in the FE-DE heterostructure can be manifested in various forms other than a single S-shaped P–V curve. In particular, a double S-shaped P–V curve is expected from the fully compensated anti-parallel domain structure, confirmed experimentally in the actual Al₂O₃/(Hf_0.5Zr_0.5)O₂/Al₂O₃ triple-layer structure. Furthermore, to reveal the origin of the double S-shaped P–V curve, a multidomain LGD model is presented. It is confirmed that this phenomenon is attributed to the evolution of inhomogeneous stray field energy.     

Binder MIMO Channels

This paper introduces a multiple-input multiple-output channel model for the characterization of a binder of telephone lines. This model is based on multiconductor transmission line theory, and uses parameters that can be obtained from electromagnetic theory or measured data. The model generates frequency-dependent channel/binder transfer function matrices as a function of cable type, geometric line-spacing and twist-length parameters, and source--load configurations. The model allows the extraction of the magnitude and the phase of individual near end crosstalk, far end crosstalk, split-pair, and phantom transfer functions from the transfer function matrix of the binder. These individual crosstalk transfer functions are often found to be very sensitive to small imperfections in the binder. Examples of category 3 twisted pair American telephone lines and ldquoquadrdquo telephone cables are also presented.