Harnessing the influence of reactive edges and defects of graphene substrates for achieving complete cycle of room-temperature molecular sensing

Molecular doping and detection are at the forefront of graphene research, a topic of great interest in physical and materials science. Molecules adsorb strongly on graphene, leading to a change in electrical conductivity at room temperature. However, a common impediment for practical applications reported by all studies to date is the excessively slow rate of desorption of important reactive gases such as ammonia and nitrogen dioxide. Annealing at high temperatures, or exposure to strong ultraviolet light under vacuum, is employed to facilitate desorption of these gases. In this article, the molecules adsorbed on graphene nanoflakes and on chemically derived graphene-nanomesh flakes are displaced rapidly at room temperature in air by the use of gaseous polar molecules such as water and ethanol. The mechanism for desorption is proposed to arise from the electrostatic forces exerted by the polar molecules, which decouples the overlap between substrate defect states, molecule states, and graphene states near the Fermi level. Using chemiresistors prepared from water-based dispersions of single-layer graphene on mesoporous alumina membranes, the study further shows that the edges of the graphene flakes (showing p-type responses to NO2 and NH3) and the edges of graphene nanomesh structures (showing n-type responses to NO2 and NH3) have enhanced sensitivity. The measured responses towards gases are comparable to or better than those which have been obtained using devices that are more sophisticated. The higher sensitivity and rapid regeneration of the sensor at room temperature provides a clear advancement towards practical molecule detection using graphene-based materials.

Nanopore processing in dielectric materials and dielectric template-assisted nanoarray synthesis : using pulsed bias to enhance process throughput and precision

An effective technique to improve the precision and throughput of energetic ion condensation through dielectric nanoporous templates and reduce nanopore clogging by using finely tuned pulsed bias is proposed. Multiscale numerical simulations of ion deposition show the possibility of controlling the dynamic charge balance on the upper template's surface to minimize ion deposition on nanopore sidewalls and to deposit ions selectively on the substrate surface in contact with the pore opening. In this way, the shapes of nanodots in template-assisted nanoarray fabrication can be effectively controlled. The results are applicable to various processes involving porous dielectric nanomaterials and dense nanoarrays.

Synthesis, mechanical and electrical properties of carbon microcoils and nanocoils

The results on the synthesis, mechanical and electrical properties of carbon microcoils and nanocoils (CMCs, CNCs) synthesized using catalytic CVD and Ni-P and Co-P catalyst alloys, respectively, are reported. SEM analysis reveals that the CMCs and CNCs have unique helical morphologies, and diameters of 5.0-9.0 μm and 450-550 nm, respectively. Moreover, CMCs with flat cross-section can be stretched to 3 times their original coil lengths. Current-voltage characteristics of a single microcoil have also been obtained. It is found that the CMCs have the electrical conductivity between 100 and 160 S/cm, whereas the electrical resistance increases by about 20% during the coil extension. Besides, the microcoils can produce light in vacuum when the test voltage reaches 10 V. The emission intensity increases as the voltage increases. The mechanical and electrical properties of CMCs and CNC make them potentially useful in many applications in micromagnetic sensors, mechanical microsprings and optoelectronics.

Nanosphere monolayer-templated, ion-assisted nanofeature etching in dielectric materials : a numerical simulation of nanoscale ion flux topography

The results of numerical simulations of nanometer precision distributions of microscopic ion fluxes in ion-assisted etching of nanoscale features on the surfaces of dielectric materials using a self-assembled monolayer of spherical nanoparticles as a mask are presented. It is shown that the ion fluxes to the substrate and nanosphere surfaces can be effectively controlled by the plasma parameters and the external bias applied to the substrate. By proper adjustment of these parameters, the ion flux can be focused onto the areas uncovered by the nanospheres. Under certain conditions, the ion flux distributions feature sophisticated hexagonal patterns, which may lead to very different nanofeature etching profiles. The results presented are generic and suggest viable ways to overcome some of the limitations of the existing plasma-assisted nanolithography.

Nanostructured copper oxide semiconductors : a perspective on materials, synthesis methods and applications

The oxides of copper (CuxO) are fascinating materials due to their remarkable optical, electrical, thermal and magnetic properties. Nanostructuring of CuxO can further enhance the performance of this important functional material and provide it with unique properties that do not exist in its bulk form. Three distinctly different phases of CuxO, mainly CuO, Cu2O and Cu4O3, can be prepared by numerous synthesis techniques including, vapour deposition and liquid phase chemical methods. In this article, we present a review of nanostructured CuxO focusing on their material properties, methods of synthesis and an overview of various applications that have been associated with nanostructured CuxO.

A meshfree particle based model for microscale shrinkage mechanisms of food materials in drying conditions

Cells are the fundamental building block of plant based food materials and many of the food processing born structural changes can fundamentally be derived as a function of the deformations of the cellular structure. In food dehydration the bulk level changes in porosity, density and shrinkage can be better explained using cellular level deformations initiated by the moisture removal from the cellular fluid. A novel approach is used in this research to model the cell fluid with Smoothed Particle Hydrodynamics (SPH) and cell walls with Discrete Element Methods (DEM), that are fundamentally known to be robust in treating complex fluid and solid mechanics. High Performance Computing (HPC) is used for the computations due to its computing advantages. Comparing with the deficiencies of the state of the art drying models, the current model is found to be robust in replicating drying mechanics of plant based food materials in microscale.

Effect of ion current density on the properties of vacuum arc-deposited TiN coatings

The influence of ion current density on the thickness of coatings deposited in a vacuum arc setup has been investigated to optimize the coating porosity. A planar probe was used to measure the ion current density distribution across plasma flux. A current density from 20 to 50 A/m2 was obtained, depending on the probe position relative to the substrate center. TiN coatings were deposited onto the cutting inserts placed at different locations on the substrate, and SEM was used to characterize the surfaces of the coatings. It was found that lowdensity coatings were formed at the decreased ion current density. A quantitative dependence of the coating thickness on the ion current density in the range of 20-50 A/m2 were obtained for the films deposited at substrate bias of 200 V and nitrogen pressure 0.1 Pa, and the coating porosity was calculated. The coated cutting inserts were tested by lathe machining of the martensitic stainless steel AISI 431. The results may be useful for controlling ion flux distribution over large industrial-scale substrates.

Measurement studies on Superhydrophobic materials

Superhydrophobicity is directly related to the wettability of the surfaces. Cassie-Baxter state relating to geometrical configuration of solid surfaces is vital to achieving the Superhydrophobicity and to achieve Cassie-Baxter state the following two criteria need to be met: 1) Contact line forces overcome body forces of unsupported droplet weight and 2) The microstructures are tall enough to prevent the liquid that bridges microstructures from touching the base of the microstructures [1]. In this paper we discuss different measurements used to characterise/determine the superhydrophobic surfaces.

High mobility diketopyrrolopyrrole (DPP)-based organic semiconductor materials for organic thin film transistors and photovoltaics

In recent years, the electron-accepting diketopyrrolopyrrole (DPP) moiety has been receiving considerable attention for constructing donor-acceptor (D-A) type organic semiconductors for a variety of applications, particularly for organic thin film transistors (OTFTs) and organic photovoltaics (OPVs). Through association of the DPP unit with appropriate electron donating building blocks, the resulting D-A molecules interact strongly in the solid state through intermolecular D-A and π-π interactions, leading to highly ordered structures at the molecular and microscopic levels. The closely packed molecules and crystalline domains are beneficial for intermolecular and interdomain (or intergranular) charge transport. Furthermore, the energy levels can be readily adjusted, affording p-type, n-type, or ambipolar organic semiconductors with highly efficient charge transport properties in OTFTs. In the past few years, a number of DPP-based small molecular and polymeric semiconductors have been reported to show mobility close to or greater than 1 cm2 V -1 s-1. DPP-based polymer semiconductors have achieved record high mobility values for p-type (hole mobility: 10.5 cm2 V-1 s-1), n-type (electron mobility: 3 cm2 V-1 s-1), and ambipolar (hole/electron mobilities: 1.18/1.86 cm2 V-1 s-1) OTFTs among the known polymer semiconductors. Many DPP-based organic semiconductors have favourable energy levels and band gaps along with high hole mobility, which enable them as promising donor materials for OPVs. Power conversion efficiencies (PCE) of up to 6.05% were achieved for OPVs using DPP-based polymers, demonstrating their potential usefulness for the organic solar cell technology. This article provides an overview of the recent exciting progress made in DPP-containing polymers and small molecules that have shown high charge carrier mobility, around 0.1 cm2 V-1 s-1 or greater. It focuses on the structural design, optoelectronic properties, molecular organization, morphology, as well as performances in OTFTs and OPVs of these high mobility DPP-based materials.

Recent progress in fluorescent blue light-emitting materials

Organic light emitting diodes (OLEDs), as an emerging technology for display and solid state lighting application, have many advantages including self-emission, lightweight, flexibility, low driving voltage, low power consumption, and low production cost. With the advancement of light emitting materials development and device architecture optimization, mobile phones and televisions based on OLED technology are already in the market. However, to obtain efficient, stable and pure blue emission than producing lower-energy colors is still one of the important subjects of these challenges. Full color and pure white light can be achieved only having stable blue emitting materials. To address this issue, significant effort has been devoted to develop novel blue light emitting materials in the past decade aiming at further improving device efficiency, color quality of emission light, and device lifetime. This review focuses on recent efforts of synthesis and device performance of small molecules, oligomers and polymers for blue emission of organic electroluminescent devices.

Electron-accepting conjugated materials based on 2-Vinyl-4,5- dicyanoimidazoles for application in organic electronics

We report the Heck coupling of 2-vinyl-4,5-dicyanoimidazole (vinazene) with selected di- and trihalo aromatics in an effort to prepare linear and branched electron-accepting conjugated materials for application in organic electronics. By selecting the suitable halo-aromatic moiety, it is possible to tune the HOMO - LUMO energy levels, absorption, and emission properties for a specific application. In this regard, materials with strong photoluminescence from blue → green → red are reported that may have potential application in organic light-emitting diodes (OLEDs). Furthermore, derivatives with strong absorption in the visible spectrum, coupled with favorable HOMO-LUMO levels, have been used to prepare promising organic photovoltaic devices (OPVs) when combined with commercially available semiconducting donor polymers.

Pyridine-incorporated dihexylquaterthiophene : a novel blue emitter for organic light emitting diodes (OLEDs)

The synthesis and characterisation of 2,5-bis(5′-hexyl-[2,2′- bithiophen]-5-yl)pyridine (Th4PY) and its use as a blue emitter in organic light emitting diodes (OLEDs) is reported. Th4PY was synthesised in high yield using a straightforward Suzuki coupling route with commercially available starting materials. As Th4PY is both soluble and has low molecular weight, blue OLEDs were fabricated using both spin-coating and vacuum deposition thin film processing techniques to study the effect of processing on device performance. OLED devices using a spin-coated layer consisting of 4′,4′′- tris(N-carbazolyl)triphenylamine (TCTA) and 2-(4-biphenylyl)-5-(4-tert- butylphenyl)-1,3,4-oxadiazole (PBD) as a host matrix together with Th4PY as emitter exhibited highly efficient sky-blue emission with a low turn-on voltage of 3V, a maximum brightness close to 15000cdm-2 at 8V, and a maximum luminous efficiency of 7.4cdA -1 (6.3lmW -1) with CIE coordinates of x≤0.212, y≤0.320. The device performance characteristics are compared using various matrices and processing techniques. The promising sky-blue OLED performance, solution processability, and ambient stability make Th4PY a promising blue emitter for application in OLEDs.

Synthesis, characterization and comparative study of thiophene- benzothiadiazole based donor-acceptor-donor (D-A-D) materials

The synthesis and characterization of solution processable donor-acceptor-donor (D-A-D) based conjugated molecules with varying ratios of thiophene as donor (D) and benzothiadiazole as acceptor (A) are reported. Optical, electrochemical, thermal, morphological and organic thin film transistor (OTFT) device properties of these materials were investigated. The thermal and polarized optical microscope analysis indicates that the materials having higher D/A ratios exhibit both liquid crystalline (LC) and OTFT behavior. AFM analysis of the materials having D/A ratios of 3 and 4 (3T1B and 4T1B) show well ordered structures, resulting from strong π-π interchain interactions compared to the other molecules in this study. A XRD patterns for 3T1B and 4T1B thin films also shows high crystalline ordering. Solution processed OTFTs of 3T1B and 4T1B have shown un-optimized charge carrier mobilities of 2 × 10 -2 cm 2 V -1 s -1 and 4 × 10 -3 cm 2 V -1 s -1, respectively on bare Si/SiO 2 substrate.

High-mobility organic thin film transistors based on benzothiadiazole- sandwiched dihexylquaterthiophenes

We report here the synthesis, characterization, and organic thin-film transistor (OTFT) mobilities of 4,7-bis(5-(5-hexylthiophen-2-yl)thiophen-2-yl) benzo[1,2,5]thiadiazole (DH-BTZ-4T). DH-BTZ-4T was prepared in one high-yield step from commercially available materials using Suzuki chemistry and purified by column chromatography. OTFTs with hole mobilities of 0.17 cm2/(Vs) and on/off current ratios of 1 × 105 were prepared from DH-BTZ-4T active layers deposited by vacuum deposition. As DH-BTZ-4T is soluble in common solvents, solution processed devices were also prepared by spin coating yielding preliminary mobilities of 6.0 × 10-3 cm 2/(Vs). The promising mobilities and low band gap (1.90 eV) coupled with solution processability and ambient stability makes this material an excellent candidate for application in organic electronics.

Isoindigo dye incorporated copolymers with naphthalene and anthracene: promising materials for stable organic field effect transistors

In this paper, we report the design and synthesis of isoindigo based low band gap polymer semiconductors, poly{N,N′-(2-octyldodecyl)-isoindigo-alt- naphthalene} (PISD-NAP) and poly{N,N′-(2-octyldodecyl)-isoindigo-alt- anthracene} (PISD-ANT). A series of donor-acceptor (D-A) copolymers can be prepared where donor and acceptor conjugated blocks can be attached alternately using organometallic coupling. In these polymers, an isoindigo dye acceptor moiety has been attached alternately with naphthalene and anthracene donor comonomer blocks by Suzuki coupling. PISD-NAP and PISD-ANT exhibit excellent solution processibility and good film-forming properties. Gel permeation chromatography exhibits a higher molecular mass with lower polydispersity. UV-vis-NIR absorption of these polymers exhibits a wide absorption band ranging from 300 nm to 800 nm, indicating the low band gap nature of the polymers. Optical band gaps calculated from the solid state absorption cutoff value for PISD-NAP and PISD-ANT are around 1.80 eV and 1.75 eV, respectively. Highest occupied molecular orbital (HOMO) values calculated respectively for PISD-NAP and PISD-ANT thin films on glass substrate by photoelectron spectroscopy in air (PESA) are 5.66 eV and 5.53 eV, indicative of the good stability of these materials in organic electronic device applications. These polymers exhibit p-channel charge transport characteristics when used as the active semiconductor in organic thin-film transistor (OTFT) devices in ambient conditions. The highest hole mobility of 0.013 cm2 V-1 s-1 is achieved in top contact and bottom-gate OTFT devices for PISD-ANT, whereas polymer PISD-NAP exhibited a hole mobility of 0.004 cm2 V -1 s-1. When these polymer semiconductors were used as a donor and PC71BM as an acceptor in OPV devices, the highest power conversion efficiency (PCE) of 1.13% is obtained for the PISD-ANT polymer.