Semiconductor Deposition via Laser Printing of a Bespoke Toner Containing Metal Xanthate Complexes.

A methodology to use laser printing, a form of electrophotography, to print metal chalcogenide complexes on paper, is described. After fusing the toner to paper, a heating step is used to cause the printed metal xanthate complexes to thermolyze within the toner and form three target metal chalcogenides: CuS, SnS, and ZnS. To achieve this, we synthesize a poly(styrene-co-n-butyl acrylate) thermopolymer that emulates the thermal properties of a commercial toner and is also solution processable with the metal xanthate complexes used: [Zn(S2COEt)2], [Cu(S2COEt)·(PPh3)2], and [Sn(S2COEt)2]. We demonstrate through energy dispersive X-ray mapping that the toner is deposited following printing and that thermolysis of the metal xanthate complexes occurs in the fused toner, demonstrating the first example of laser printing of inorganic complexes and, in turn, semiconductors.

A rich gallery of carbon dots based photoluminescent suspensions and powders derived by citric acid/urea.

In this study we demonstrate simple guidelines to generate a diverse range of fluorescent materials in both liquid and solid state by focusing on the most popular C-dots precursors, i.e. the binary systems of citric acid and urea. The pyrolytic treatment of those precursors combined with standard size separation techniques (dialysis and filtration), leads to four distinct families of photoluminescent materials in which the emissive signal predominantly arises from C-dots with embedded fluorophores, cyanuric acid-rich C-dots, a blend of molecular fluorophores and a mixture of C-dots with unbound molecular fluorophores, respectively. Within each one of those families the chemical composition and the optical properties of their members can be fine-tuned by adjusting the molar ratio of the reactants. Apart from generating a variety of aqueous dispersions, our approach leads to highly fluorescent powders derived from precursors comprising excessive amounts of urea that is consumed for the build-up of the carbogenic cores, the molecular fluorophores and the solid diluent matrix that suppresses self-quenching effects.

Textile materials inspired by structural colour in nature.

The concept of mimicking structural colour in nature as an alternative to traditional textile coloration techniques would reduce dependency on dyes, pigments and vast quantities of water in the textile supply chain. Structural colours originate from the physical interaction of light with nanoscale structures. This is exhibited in the bodies and wings of certain species of butterfly, beetles and plants. The angular optical effects of the Chrysina gloriosa beetle result from the periodicity due to the cholesteric liquid crystal (CLC) structure adopted by the cells in their exoskeleton. The optical properties of CLCs makes promising applications for optical sensors and anti-counterfeit materials. Application using inkjet printing technology enables designs to be tuned to meet product requirements, and with a hydrophobic treatment challenges associated with a rough surface such as textiles are overcome. Here we report inkjet printing CLC solutions onto hydrophobic pre-treated textiles. CIE L*a*b* values demonstrate the resultant colourful films display a greater degree of colour compared to those on untreated textiles.

Layer by Layer Antimicrobial Coatings Based on Nafion, Lysozyme, and Chitosan.

The study focuses on the development of a new family of layer-by-layer coatings comprising Nafion, lysozyme and chitosan to address challenges related to microbial contamination. Circular dichroism was employed to gain insights on the interactions of the building blocks at the molecular level. Quartz crystal microbalance tests were used to monitor in real time the build-up of multilayer coatings, while atomic force microscopy, contact angle and surface zeta potential measurements were performed to assess the surface characteristics of the multilayer assemblies. Remarkably, the nanocoated surfaces show almost 100% reduction in the population of both Escherichia coli and Staphylococcus aureus. The study suggests that Nafion based synergistic platforms can offer an effective line of defence against bacteria, facilitating antimicrobial mechanisms that go beyond the concept of exclusion zone.

Initial Studies Directed toward the Rational Design of Aqueous Graphene Dispersants.

This study presents preliminary experimental data suggesting that sodium 4-(pyrene-1-yl)butane-1-sulfonate (PBSA), 5, an analogue of sodium pyrene-1-sulfonate (PSA), 1, enhances the stability of aqueous reduced graphene oxide (RGO) graphene dispersions. We find that RGO and exfoliated graphene dispersions prepared in the presence of 5 are approximately double the concentration of those made with commercially available PSA, 1. Quantum mechanical and molecular dynamics simulations provide key insights into the behavior of these molecules on the graphene surface. The seemingly obvious introduction of a polar sulfonate head group linked via an appropriate alkyl spacer to the aromatic core results in both more efficient binding of 5 to the graphene surface and more efficient solvation of the polar head group by bulk solvent (water). Overall, this improves the stabilization of the graphene flakes by disfavoring dissociation of the stabilizer from the graphene surface and inhibiting reaggregation by electrostatic and steric repulsion. These insights are currently the subject of further investigations in an attempt to develop a rational approach to the design of more effective dispersing agents for rGO and graphene in aqueous solution.

Plasma-Etched Pattern Transfer of Sub-10 nm Structures Using a Metal-Organic Resist and Helium Ion Beam Lithography.

Field-emission devices are promising candidates to replace silicon fin field-effect transistors as next-generation nanoelectronic components. For these devices to be adopted, nanoscale field emitters with nanoscale gaps between them need to be fabricated, requiring the transfer of, for example, sub-10 nm patterns with a sub-20 nm pitch to substrates like silicon and tungsten. New resist materials must therefore be developed that exhibit the properties of sub-10 nm resolution and high dry etch resistance. A negative tone, metal-organic resist is presented here. It can be patterned to produce sub-10 nm features when exposed to helium ion beam lithography at line doses on the order of tens of picocoulombs per centimeter. The resist was used to create 5 nm wide, continuous, discrete lines spaced on a 16 nm pitch in silicon and 6 nm wide lines on an 18 nm pitch in tungsten, with line edge roughness of 3 nm. After the lithographic exposure, the resist demonstrates high resistance to silicon and tungsten dry etch conditions (SF6 and C4F8 plasma), allowing the pattern to be transferred to the underlying substrates. The resist's etch selectivity for silicon and tungsten was measured to be 6.2:1 and 5.6:1, respectively; this allowed 3 to 4 nm thick resist films to yield structures that were 21 and 19 nm tall, respectively, while both maintained a sub-10 nm width on a sub-20 nm pitch.

Comment on: Synthesis of New Azo Compounds Based on N-(4-Hydroxyphenyl)maleimide and N-(4-Methylphenyl)maleimide. Molecules 2010, 15, 7498-7508.

The synthesis of (E)-phenylazo-3-N-(4-hydroxyphenyl)maleimide (1) using a procedure previously reported in Molecules is deemed to be erroneous. A detailed re-investigation of the earlier work suggests that the spectral data for key intermediates and the final product, (1), was mis-assigned. We conclude that compound (1) was not synthesized, but rather an unusual ring opening reaction of the maleimide unit of the starting material, N-(4-hydroxyphenyl)maleimide (2) leading to the generation of (Z)-4-((4-hydroxyphenyl)amino)-4-oxobut-2-enoic acid, (3) was observed instead. Examination of the original experimental data reveals systematic errors in the reporting of all of the combustion microanalytical data. Overall, the present investigation suggests that errors in the interpretation of spectral data, falsification of analytical data and selective editing of experimental results raise questions over the veracity of the work presented in the original paper.

All Inkjet-Printed Graphene-Silver Composite Ink on Textiles for Highly Conductive Wearable Electronics Applications.

Inkjet-printed wearable electronic textiles (e-textiles) are considered to be very promising due to excellent processing and environmental benefits offered by digital fabrication technique. Inkjet-printing of conductive metallic inks such as silver (Ag) nanoparticles (NPs) are well-established and that of graphene-based inks is of great interest due to multi-functional properties of graphene. However, poor ink stability at higher graphene concentration and the cost associated with the higher Ag loading in metal inks have limited their wider use. Moreover, graphene-based e-textiles reported so far are mainly based on graphene derivatives such as graphene oxide (GO) or reduced graphene oxide (rGO), which suffers from poor electrical conductivity. Here we report inkjet printing of highly conductive and cost-effective graphene-Ag composite ink for wearable e-textiles applications. The composite inks were formulated, characterised and inkjet-printed onto PEL paper first and then sintered at 150 °C for 1 hr. The sheet resistance of the printed patterns is found to be in the range of ~0.08-4.74 Ω/sq depending on the number of print layers and the graphene-Ag ratio in the formulation. The optimised composite ink was then successfully printed onto surface pre-treated (by inkjet printing) cotton fabrics in order to produce all-inkjet-printed highly conductive and cost-effective electronic textiles.

An Exploration of Behind-the-Ear ECG Signals From a Single Ear Using Inkjet Printed Conformal Tattoo Electrodes.

Wearable sensors placed behind-the-ear are emerging as being very promising for unobtrusive long term monitoring. Factors such as gait, electroencephalography (EEG), and ballistocardiography (BCG) can all be measured from behind-the-ear in a socially acceptable hearing aid based form factor. Previous works have investigated the recording of electrocardiography (ECG) from the ear, but generally with one electrode placed some distance away from the ear itself. This paper uses recently introduced tattoo electrodes to investigate whether ECG components can indeed be measured from behind a single ear. Compared to a reference photophelsmography (PPG) device we show that the fundamental heart beat frequency is present in behind-the-ear ECG only in half of the cases considered. In contrast the second harmonic is present in all records and could allow the extraction of heart rate to within a few beats-per-minute accuracy. Further signal processing work is required to allow the automated extraction of this, particularly when working with short time windows of data, but our results characterize the signal and demonstrate the principle of behind-the-ear ECG collected from a single ear.

Use of Supramolecular Assemblies as Lithographic Resists.

A new resist material for electron beam lithography has been created that is based on a supramolecular assembly. Initial studies revealed that with this supramolecular approach, high-resolution structures can be written that show unprecedented selectivity when exposed to etching conditions involving plasmas.

Submicron Patterning of Polymer Brushes: An Unexpected Discovery from Inkjet Printing of Polyelectrolyte Macroinitiators.

Using an electrostatic-based super inkjet printer we report the high-resolution deposition of polyelectrolyte macroinitiators and subsequent polymer brush growth using SI-ARGET-ATRP. We go on to demonstrate for the first time a submicron patterning phenomenon through the addition of either a like charged polyelectrolyte homopolymer or through careful control of ionic strength. As a result patterning of polymer brushes down to ca. 300 nm is reported. We present a possible mechanistic model and consider how this may be applied to other polyelectrolyte-based systems as a general method for submicron patterning.

Reducing dynamic disorder in small-molecule organic semiconductors by suppressing large-amplitude thermal motions.

Thermal vibrations and the dynamic disorder they create can detrimentally affect the transport properties of van der Waals bonded molecular semiconductors. The low-energy nature of these vibrations makes it difficult to access them experimentally, which is why we still lack clear molecular design rules to control and reduce dynamic disorder. In this study we discuss the promising organic semiconductors rubrene, 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothio-phene and 2,9-di-decyl-dinaphtho-[2,3-b:20,30-f]-thieno-[3,2-b]-thiophene in terms of an exceptionally low degree of dynamic disorder. In particular, we analyse diffuse scattering in transmission electron microscopy, to show that small molecules that have their side chains attached along the long axis of their conjugated core are better encapsulated in their crystal structure, which helps reduce large-amplitude thermal motions. Our work provides a general strategy for the design of new classes of very high mobility organic semiconductors with a low degree of dynamic disorder.

Conformal electronics for longitudinal bio-sensing in at-home assistive and rehabilitative devices.

Wearable electronics are revolutionizing personalized and preventative healthcare by allowing the easy, unobtrusive, and long term monitoring of a range of body parameters. Conformal electronics which attach directly to the skin in a very robust and long term manner are envisioned as the next generation of highly portable miniaturized computing devices, beyond wearables. In this paper we overview the state-of-the-art in conformal electronics created using silver nanoparticle inkjet printed techniques for home assistive and rehabilitative devices. The barriers to wider adaption, particularly the challenges of high performance antenna design when placed close to the body, are discussed in detail.

Non-linear, cata-Condensed, Polycyclic Aromatic Hydrocarbon Materials: A Generic Approach and Physical Properties.

A generic approach to the regiospecific synthesis of halogenated polycyclic aromatics is made possible by the one- or two-directional benzannulation reactions of readily available (ortho-allylaryl)trichloroacetates (the "BHQ" reaction). Palladium-catalysed cross-coupling reactions of the so-formed haloaromatics enable the synthesis of functionalised polycyclic aromatic hydrocarbons (PAHs) with surgical precision. Overall, this new methodology enables the facile mining of chemical space in search of new electronic functional materials.

Effect of oxygen, moisture and illumination on the stability and reliability of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) OTFTs during operation and storage.

We report a systemic study of the stability of organic thin film transistors (OTFTs) both in storage and under operation. Apart from a thin polystyrene buffer layer spin-coated onto the gate dielectric, the constituent parts of the OTFTs were all prepared by vacuum evaporation. The OTFTs are based on the semiconducting small molecule dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) deposited onto the surface of a polystyrene-buffered in situ polymerized diacrylate gate insulator. Over a period of 9 months, no degradation of the hole mobility occurred in devices stored either in the dark in dry air or in uncontrolled air and normal laboratory fluorescent lighting conditions. In the latter case, rather than decreasing, the mobility actually increased almost 2-fold to 1.5 cm(2)/(V · s). The devices also showed good stability during repeat on/off cycles in the dark in dry air. Exposure to oxygen and light during the on/off cycles led to a positive shift of the transfer curves due to electron trapping when the DNTT was biased into depletion by the application of positive gate voltage. When operated in accumulation, negative gate voltage under the same conditions, the transfer curves were stable. When voltage cycling in moist air in the dark, the transfer curves shifted to negative voltages, thought to be due to the generation of hole traps either in the semiconductor or its interface with the dielectric layer. When subjected to gate bias stress in dry air in the dark for at least 144 h, the device characteristics remained stable.

Segregation in like-charged polyelectrolyte-surfactant mixtures can be precisely tuned via manipulation of the surfactant mass ratio.

In this study, we consider segregative phase separation in aqueous mixtures of quaternary ammonium surfactants didecyldimethylammonium chloride (DDQ) and alkyl (C12, 70%; C14 30%) dimethyl benzyl ammonium chloride (BAC) upon the addition of poly(diallyldimethylammonium) chloride (pDADMAC) as a function of both concentration and molecular weight. The nature of the surfactant type is dominant in determining the concentration at which separation into an upper essentially surfactant-rich phase and lower polyelectrolyte-rich phase is observed. However, for high-molecular-weight pDADMAC there is a clear indication of an additional depletion flocculation effect. When the BAC/DDQ ratio is tuned, the segregative phase separation point can be precisely controlled. We propose a phase separation mechanism for like-charged quaternary ammonium polyelectrolyte/surfactant/water mixtures induced by a reduction in the ionic atmosphere around the surfactant headgroup and possible ion pair formation. An additional polyelectrolyte-induced depletion flocculation effect was also observed.

An Approach to the Synthesis of Functionalized Polycyclic Aromatic Hydrocarbons.

The application of a new benzannulation reaction for the regiocontrolled synthesis of functionalized chrysenes is reported. The initial benzannulation and the subsequent halogen displacement reactions are both highly regiospecific, which thereby enables the regiocontrolled synthesis of a variety of 4,10-disubstituted chrysenes from commercially available 1,5-dihydroxynaphthalene.

Solubilisation capacity of Brij surfactants.

The aim of this study was to investigate the potential of selected Brij non-ionic surfactants for enhancing the solubility of poorly water-soluble drugs. Griseofulvin was selected as a model drug candidate enabling comparisons to be made with the solubilisation capacities of other poly(ethylene oxide)-based copolymers. UV/Vis and (1)H NMR spectroscopies were used to quantify the enhancement of solubility of griseofulvin in 1 wt% aqueous micellar solutions of Brij 78 (C(18)H(37)E(20)), Brij 98 (C(18)H(35)E(20)) and Brij 700 (C(18)H(37)E(100)) (where E represents the OCH(2)CH(2) unit of the poly(ethylene oxide) chain) at 25, 37 and 40 °C. Solubilisation capacities (S(cp) expressed as mg griseofulvin per g Brij) were similar for Brij 78 and 98 (range 6-11 mg g(-1)) but lower for Brij 700 (3-4 mg g(-1)) as would be expected for the surfactant with the higher ethylene oxide content. The drug loading capacity of micelles of Brij 78 was higher than many di- and triblock copolymers with hydrophilic E-blocks specifically designed for enhancement of drug solubility.

Effect of water-soluble polymers, polyethylene glycol and poly(vinylpyrrolidone), on the gelation of aqueous micellar solutions of Pluronic copolymer F127.

The micellization of F127 (E(98)P(67)E(98)) in dilute aqueous solutions of polyethylene glycol (PEG6000 and PEG35000) and poly(vinylpyrrolidone) (PVP K30 and PVP K90) is studied. The average hydrodynamic radius (r(h,app)) obtained from the dynamic light scattering technique increased with increase in PEG concentration but decreased on addition of PVP, results which are consistent with interaction of the micelles with PEG and the formation of micelles clusters, but no such interaction occurs with PVP. Tube inversion was used to determine the onset of gelation. The critical concentration of F127 for gelation increased on addition of PEG and of PVP K30 but decreased on addition of PVP K90. Small-angle X-ray scattering (SAXS) was used to show that the 30 wt% F127 gel structure (fcc) was independent of polymer type and concentration, as was the d-spacing and so the micelle hard-sphere radius. The maximum elastic modulus (G(max)(')) of 30 wt% F127 decreased from its value for water alone as PEG was added, but was little changed by adding PVP. These results are consistent with the packed-micelles in the 30 wt% F127 gel being effectively isolated from the polymer solution on the microscale while, especially for the PEG, being mixed on the macroscale.

The effect of water-soluble polymers, PEG and PVP, on the solubilisation of griseofulvin in aqueous micellar solutions of Pluronic F127.

The purpose of this study was to investigate the possibility of enhancing the solubilisation capacity of micellar solutions of Pluronic F127 for the poorly water-soluble drug griseofulvin by co-formulating with a water-soluble polymer. The effect of the addition of the polyethylene glycols PEG6000 and 35000, and the poly(vinylpyrrolidone)s PVP K30 and K90, on the solubilisation capacity of 1wt% solutions of Pluronic F127 was related to the effect of these additives on particle size as determined by dynamic light scattering measurements. The addition of PEG35000 to 1wt% F127 solutions significantly increased the solubility capacity expressed in terms of unit weight of F127; PVP K90 had a smaller effect but no enhancement was noted following the addition of PEG6000 or PVP K30. Solubilisation enhancement was thought to be a consequence of the association of the polymers with the E-blocks of the micelle corona so providing an expanded region of reduced polarity for drug solubilisation.