Synthesis and Electrochemical Characterization of Nitrate-Doped Polypyrrole/Ag Nanowire Nanorods as Supercapacitors.

Polypyrrole (PPy)-capped silver nanowire (Ag NW) nanomaterials (core-shell rod-shaped Ag NW@PPy) were synthesized using a one-port suspension polymerization technique. The thickness of the PPy layer on the 50 nm thickness/15 µm length Ag NW was effectively controlled to 10, 40, 50, and 60 nm. Thin films cast from one-dimensional conductive Ag NW@PPy formed a three-dimensional (3D) conductive porous network structure and provided excellent electrochemical performance. The 3D Ag NW@PPy network can significantly reduce the internal resistance of the electrode and maintain structural stability. As a result, a high specific capacitance of 625 F/g at a scan rate of 1 mV/s was obtained from the 3D porous Ag NW@PPy composite film. The cycling performance over a long period exceeding 10,000 cycles was also evaluated. We expect that our core-shell-structured Ag NW@PPy composites and their 3D porous structure network films can be applied as electrochemical materials for the design and manufacturing of supercapacitors and other energy storage devices.

Flexible Sensor Film Based on Rod-Shaped SWCNT-Polypyrrole Nanocomposite for Acetone Gas Detection.

A nanocomposite rod-shaped structure with a single-walled carbon nanotube (SWCNT) embedded in polypyrrole (PPy) doped with nonafluorobutanesulfonic acid (C4F), SWCNT/C4F-PPy, was synthesized using emulsion polymerization. The hybrid ink was then directly coated on a polyimide film interdigitated with the Cu/Ni/Au electrodes via a screen-printing technique to create a flexible film sensor. The sensor film showed a response of 1.72% at 25 °C/atmospheric pressure when acetone gas of 5 ppm was injected, which corresponds to almost 95% compared to the Si wafer-based array interdigitated with the Au electrode. Additionally, C4F was used as a hydrophobic dopant of PPy to improve the stability of humidity and to produce a highly sensitive film-type gas sensor that provides stable detection even in humid conditions.

A high sensitivity acetone gas sensor based on polyaniline-hydroxypropyl methylcellulose core-shell-shaped nanoparticles.

Core-shell-shaped nanoparticles (CSS-NPs) with polyaniline emeraldine salts (PANi) in the core and hydroxypropyl methylcellulose (HPMC) and heptadecafluorooctanesulfonic acid (C8F) shells, i.e., C8F-doped PANi@HPMC CSS-NPs, were synthesized as a gaseous acetone sensing material with high sensitivity and humidity stability. The HPMC was chemically combined on the positively charged PANi NPs' outer surface, allowing it to efficiently detect acetone gas at concentrations as low as 50 ppb at 25 °C. To impart humidity stability, C8F was employed as a hydrophobic dopant, and a valid signal could be reliably detected even in the range of 0-80% relative humidity. The sensing material's structural analysis was conducted using scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and infrared spectroscopy, and in particular, the reaction mechanism with acetone gas was detected through a spectroscopic method. Thus, these findings illustrate the potential as a novel sensing material to detect acetone gas at a trace level of less than 1 ppm in human respiratory gas.

Acetone Gas Sensor Based on SWCNT/Polypyrrole/Phenyllactic Acid Nanocomposite with High Sensitivity and Humidity Stability.

We synthesized core-shell-shaped nanocomposites composed of a single-walled carbon nanotube (SWCNT) and heptadecafluorooctanesulfonic acid-doped polypyrrole (C8F-doped-PPy)/phenyllatic acid (PLA), i.e., C8F-doped-PPy/PLA@SWCNT, for detecting acetone gas with high sensitivity and humidity stability. The obtained nanocomposites have the structural features of a sensing material as a C8F-doped-PPy layer surrounding a single-stranded SWCNT, and a PLA layer on the outer surface of the PPy as a specific sensing layer for acetone. PLA was chemically combined with the positively charged PPy backbone and provided the ability to reliably detect acetone gas at concentrations as low as 50 ppb even at 25 °C, which is required for medical diagnoses via human breath analysis. When C8F was contained in the pyrrole monomer in a ratio of 0.1 mol, it was able to stably detect an effective signal in a relative humidity (RH) of 0-80% range.

Stretchable and High-performance Sensor films Based on Nanocomposite of Polypyrrole/SWCNT/Silver Nanowire.

We report the fabrication of stretchable sensor films (SSF) using a composite of functionalized polypyrrole- single-walled carbon nanotube (SWCNT)-silver nanowire hybrid networks embedded into a cross-linked polydimethylsiloxane elastomer. The SSF exhibited low resistivity of 30 Ω/sq and an outstanding mechanical elasticity of up to 25% (no visible change in the sheet resistance after 100 cycle at stretching-release test of 25%). These SSFs were responsive to 1 ppm ammonia gas even at a low temperature of 40 °C with 20% relative humidity and also maintained reproducibility and reversibility when repeatedly exposed to ammonia gas more than 100 times. In addition, it was confirmed that the sensor film was hardly affected even at a relative humidity range of 20% to 80%.

Stretchable and Low-Haze Ag-Nanowire-Network 2-D Films Embedded into a Cross-linked Polydimethylsiloxane Elastomer.

We report the fabrication of stretchable transparent electrode films (STEF) using 15-nm-diameter Ag nanowires networks embedded into a cross-linked polydimethylsiloxane elastomer. 15-nm-diameter Ag NWs with a high aspect ratio (˃1000) were synthesized through pressure-induced polyol synthesis in the presence of AgCl particles with KBr. These Ag NW network-based STEF exhibited considerably low haze values (<1.5%) with a transparency of 90% despite the low sheet resistance of 20 Ω/sq. The STEF exhibited an outstanding mechanical elasticity of up to 20% and no visible change occurred in the sheet resistance after 100 cycles at a stretching-release test of 20%.

Ambient-Stable and Durable Conductive Ag-Nanowire-Network 2-D Films Decorated with a Ti Layer.

Highly stable and durable conductive silver nanowire (Ag NW) network electrode films were prepared through decoration with a 5-nm-thick Ti layer. The Ag NW network 2-D films showed sheet resistance values as low as 32 ohm/sq at 88% transparency when decorated with Ti. These 2-D films exhibited a 30% increase in electrical conductivity while maintaining good stability of the films through enhanced resistance to moisture and oxygen penetration as a result of the protective effect of the Ti layer.

Electrical conductivity of poly(3,4-ethylenedioxythiophene):p-toluene sulfonate films hybridized with reduced graphene oxide.

Reduced graphene oxide-poly(3,4-ethylenedioxythiophene):p-toluene sulfonate (rGO-PEDOT:PTS) hybrid electrode films were synthesized directly on a substrate by interfacial polymerization between an oxidizing solid layer and liquid droplets of 3,4-ethylenedioxythiophene (EDOT) produced by electrospraying. The EDOT reduced the graphene oxide by donating electrons during its transformation into PEDOT:PTS, and hybrid films consisting of rGO distributed in a matrix of PEDOT:PTS were obtained. These rGO-PEDOT:PTS hybrid films showed excellent electrical conductivities as high as 1,500 S/cm and a sheet resistance of 70 Ω sq(-1). The conductivity values are up to 50% greater than those of films containing conductive PEDOT:PTS alone. These results confirm that highly conductive rGO-PEDOT:PTS hybrid films can potentially be used as organic transparent electrodes.

Thin and long silver nanowires self-assembled in ionic liquids as a soft template: electrical and optical properties.

Thin and long silver nanowires were successfully synthesized using the polyvinylpyrrolidone (PVP)-assisted polyol method in the presence of ionic liquids, tetrapropylammonium chloride and tetrapropylammonium bromide, which served as soft template salts. The first step involved the formation of Ag nanoparticles with a diameter of 40 to 50 nm through the reduction of silver nitrate. At the growing stage, the Ag nanoparticles were converted into thin and long one-dimensional wires, with uniform diameters of 30 ± 3 nm and lengths of up to 50 µm. These Ag nanowires showed an electrical conductivity of 0.3 × 10(5) S/cm, while the sheet resistance of a two-dimensional percolating Ag nanowire network exhibited a value of 20 Ω/sq with an optical transmittance of 93% and a low haze value.

Structures and properties of poly(3-alkylthiophene) thin-films fabricated though vapor-phase polymerization.

Organic semiconducting polymer thin-films of 3-hexylthiophene, 3-octylthiophene, 3-decylthiophene, containing highly oriented crystal were fabricated by gas-phase polymerization using the CVD technique. These poly(3-alkylthiophene) films had a crystallinity up to 80%, and possessed a Hall mobility up to 10 cm2/Vs. The degree of crystalinity and the mobility values increased as the alkyl chain length increased. The crystal structure of the polymers was composed of stacked layers constructed by a side-by-side arrangement of alkyl chains and in-plane pi-pi stacking. These thin films are capable of being applied to organic electronics as the active materials used in thin-film transistors and organic photovoltaic cells.

Variety of nanopatterns on different substrates using PS-b-PMMA and their applications.

High density arrays of nanostructures over a large area can be formed on a range of substrates, such as glass, GaN, SiO2 deposited silicon wafer, etc. by the self-assembly of PS-b-PMMA block copolymers. The morphology of the polymer surface is strongly dependent on the thickness of the polymer layer. It is necessary to control the size and shape in order to get the desired properties. The deposition of a gold thin film on polymer-patterned glass followed by the removal of the remaining part of the polymer results in patterned gold on glass, which can be used as a transparent conducting electrode, where the conductivity and transparency depends on the thickness of gold and as well as on the connectivity of the gold pattern. Similarly, the polymer pattern can be transferred to an underlying GaN layer in an as grown LED, which increases the photoluminescence intensity making it useful as a photonic crystal.

Fabrication of 2D photonic crystals using block copolymer patterns on as grown LEDs.

Di-block copolymer polystyrene-block-polymethyl methacrylate (PS-b-PMMA) was used to make patterns over a large area of as grown LEDs. The polymer patterns on LEDs surface could be transferred to the underlying p-GaN, the topmost layer of as grown LEDs by both reactive ion etching (RIE) and photo-enhanced chemical (PEC) etching. Removal of remaining polymer chains results in patterned LEDs which shows higher light extraction efficiency. In our experiment, much higher intensity for patterned LEDs in both photoluminescence (PL) and electroluminescence (EL) data plot were found. Similar improvements were found in I-V and L-I curves for patterned LEDs.

Fabrication of nanopatterns using block copolymer and controlling surface morphology.

This paper reports an approach for patterning substrates on the nanoscale using a block copolymer, polystyrene-b-polymethylmethacrylate (PS-b-PMMA), which forms cylindrical microdomains. The morphology of the polymer surface was strongly dependent on the thickness of the polymer layer. Spin coating the polymer solution onto the substrate followed by baking resulted in the self-assembly of the components of the polymer. Exposure to ultraviolet radiation degraded the PMMA chain, which could be removed by rinsing in acetic acid to give patterned holes. However, the small size of the hole limits the applications of the template. This problem was solved by sonicating the sample in different solutions in a series of steps to produce a fingerprint pattern or patterns containing PS cylindrical domains having large interstitial spaces with an average of >30 nm. The morphology of the polymer film surface was examined by atomic force microscopy (AFM) and scanning electron microscopy (SEM).

50 nm DNA nanoarrays generated from uniform oligonucleotide films.

One of the most challenging but potentially rewarding goals in nanoscience is the ability to direct the assembly of nanoscale materials into functional architectures with high yields, minimal steps, and inexpensive procedures. Despite their unique physical properties, the inherent difficulties of engineering wafer-level arrays of useful devices from nanoscale materials in a cost-effective manner have provided serious roadblocks toward technological impact. To address nanoscale features while still maintaining low fabrication costs, we demonstrate here an inexpensive printing method that enables repeated patterning of large-area arrays of nanoscale materials. DNA strands were patterned over 4 mm areas with 50 nm resolution by a soft-lithographic subtraction printing process, and DNA hybridization was used to direct the assembly of sub-20 nm materials to create highly ordered two-dimensional nanoparticle arrays. The entire printing and assembly process was accomplished in as few as three fabrication steps and required only a single lithographically templated silicon master that could be used repeatedly. The low-cost procedures developed to generate nanoscale DNA patterns can be easily extended toward roll-to-roll assembly of nanoscale materials with sub-50 nm resolution and fidelity.

Controllable feature sizes of highly conductive poly(3,4-ethylenedioxythiophene) nanofilms patterned on SiO2 surface.

In this paper, we report a novel patterning method for a poly(3,4-ethylenedioxythiophene) (PEDOT) nanofilm deposited on an OTS monolayer-coated silicon wafer substrate by the vapor phase polymerization method. To scrutinize the adhesion improvement, electrical conductivity and feature controllability, patterned PEDOT nanofilms were investigated with a Scotch tape peel test, I-V curve measurement, and optical and atomic force microscopes. The scrutinization strongly indicates that the adhesion improvement is most likely due to direct chemical bonds formed between ethylenedioxythiophene (EDOT) molecules and photo-oxidized OTS monolayer during a vapor phase polymerization reaction. The investigation also discovered that the feature size of the film can be chemically controlled by the reaction between OTS and reactive atomic oxygen gases, and the patterned films generally show a noticeably good electrical conductivity (approximately 500 S/cm at merely approximately 100 nm thick film). These results successfully demonstrate that the patterned PEDOT nanofilms are qualified enough to be employed as an electrode component of an OTFT device since the electrode materials must show an electrical conductivity of at least 50 S/cm or higher.