Molecular engineering of nine closely related copper(II) N,N-disubstituted-N'-acylthiourea complexes (single source precursors containing pre-organised Cu-S bonding motifs) has enabled systematic optimisation of their volatilisation behaviour and thermal stability. The influence of ligand substituents, steric branching, and solid-state geometry on precursor performance was examined. All complexes are monomeric and exhibit high thermal stability, with tuneable volatility arising from structural modifications to the acylthiourea backbone. Based on thermal and vapour pressure analysis, the most promising candidates were selected for proof-of-concept solvent free Chemical Vapour Deposition (CVD), representing the first use of this ligand class in a purely thermal deposition process; previous reports employed only aerosol-assisted CVD. Under these conditions the precursors yielded a copper rich digenite (Cu1.8S) nanocrystalline material; with a minor covellite (CuS) contribution observed, likely arising from an incompletely converted surface layer. Vapour pressure measurements demonstrate that, through appropriate ligand design, an equilibrium vapour pressure of ≈0.1 Torr can be achieved without compromising precursor stability. These results highlight N,N-disubstituted-N'-acylthiourea complexes as a versatile and tuneable platform for single-source precursor development.

Miniaturization is the trend to manufacture ever smaller devices and this process requires knowledge, experience, understanding of materials, manufacturing techniques and scaling laws. The fabrication techniques used in semiconductor industry deliver an exceptionally high yield of devices and provide a well-established platform. Today, these miniaturized devices are manufactured with high reproducibility, design flexibility, scalability and multiplexed features to be used in several applications including micro-, nano-fluidics, implantable chips, diagnostics/biosensors and neural probes. We here provide a review on the microfabricated devices used for biology driven science. We will describe the ubiquity of the use of micro-nanofabrication techniques in biology and biotechnology through the fabrication of high-aspect-ratio devices for cell sensing applications, intracellular devices, probes developed for neuroscience-neurotechnology and biosensing of the certain biomarkers. Recently, the research on micro and nanodevices for biology has been progressing rapidly. While the understanding of the unknown biological fields -such as human brain- has been requiring more research with advanced materials and devices, the development protocols of desired devices has been advancing in parallel, which finally meets with some of the requirements of biological sciences. This is a very exciting field and we aim to highlight the impact of micro-nanotechnologies that can shed light on complex biological questions and needs.

The importance of understanding the growth fundamentals of ZnO/TiO2nanolaminate structures deposited by atomic layer deposition is explored.

Chitosan-based films have a diverse range of potential applications but are currently limited in terms of commercial use due to a lack of methods specifically designed to produce thin films in high volumes. To address this limitation directly, hydrogels prepared from chitosan, chitosan-tetraethoxy silane, also known as tetraethyl orthosilicate (TEOS) and chitosan-glutaraldehyde have been used to prepare continuous thin films using a slot-die technique which is described in detail. By way of preliminary analysis of the resulting films for comparison purposes with films made by other methods, the mechanical strength of the films produced was assessed. It was found that as expected, the hybrid films made with TEOS and glutaraldehyde both show a higher yield strength than the films made with chitosan alone. In all cases, the mechanical properties of the films were found to compare very favorably with similar measurements reported in the literature. In order to assess the possible influence of the direction in which the hydrogel passes through the slot-die on the mechanical properties of the films, testing was performed on plain chitosan samples cut in a direction parallel to the direction of travel and perpendicular to this direction. It was found that there was no evidence of any mechanical anisotropy induced by the slot die process. The examples presented here serve to illustrate how the slot-die approach may be used to create high-volume, high-area chitosan-based films cheaply and rapidly. It is suggested that an approach of the type described here may facilitate the use of chitosan-based films for a wide range of important applications.

The bottom-up colloidal synthesis of photonic band gap (PBG) materials or photonic crystals (PCs) has attracted considerable interest in comparison to top-down approaches due to the relatively simple processing steps involved, the potential for large area sample production and the relatively low-costs associated with this approach for the fabrication of complex 3-dimensional (3D) structures. This research focuses on the colloidal synthesis of poly(methyl methacrylate) (PMMA)@Au core-shell (CS) structures, their bottom-up assembly into 3D metallodielectric PCs (MDPCs) and the demonstration of their potential to be used as surface enhanced Raman substrates (SERS) using the commonly deployed SERS reporter molecule, 4-aminothiolphenol. Here, monodispersed spherical PMMA particles were used both as a host material for Au nanoparticles (NPs) and as a crystal template to produce the MDPC structures. The materials engineering employed which involved combining the synthesis of monodispersed CS particles and the fabrication of their corresponding MDPCs enabled us to control the distribution of Au NPs in the PC structure and thereby investigate their light scattering, reflection and transmission properties including Raman scattering.

A series of Aurivillius phase materials,Bi 5 Ti 3-2x Fe 1+x NbxO 15 (x = 0, 0.1, 0.2, 0.3, and 0.4), was fabricated by chemical solution deposition. The effects of aliovalent substitution for the successful inclusion of Fe 3+ and Nb 5+ by replacing Ti 4+ were explored as a potential mechanism for increasing magnetic ion content within the material. The structural, optical, piezoelectric, and magnetic properties of the materials were investigated. It was found that a limit of x = 0.1 was achieved before the appearance of secondary phases as determined by the X-ray diffraction. Absorption in the visible region increased with increasing values of x corresponding to the transition from the valence band to the conduction band of the Fe-eg energy level. Piezoresponse force microscopy measurements demonstrated that the lateral piezoelectric response increased with increasing values of x. Magnetic measurements of Bi 5 Ti 3-2x Fe 1+x NbxO 15 exhibited a weak ferromagnetic response at 2, 150, and 300 K of 2.2, 1.6, and 1.5 emu/cm 3 with Hc of ~40, 36, and 34 Oe, respectively. The remanent magnetization MR of this sample was found to be higher than the range of reported values for the Bi 5 Ti 3 Fe 1 O 15 parent phase. Elemental analysis of this sample by energy-dispersive X-ray analysis did not provide any evidence for the presence of iron-rich secondary phases. However, it is noted that a series of measurements at varying sample volumes and instrument resolutions is still required in order to put a defined confidence levelon the Bi 5 Ti 2.8 Fe 1.1 Nb 0.1 O 15 material being a single-phase multiferroic.

The research field of glucose biosensing has shown remarkable growth and development since the first reported enzyme electrode in 1962. Extensive research on various immobilization methods and the improvement of electron transfer efficiency between the enzyme and the electrode have led to the development of various sensing platforms that have been constantly evolving with the invention of advanced nanostructures and their nano-composites. Examples of such nanomaterials or composites include gold nanoparticles, carbon nanotubes, carbon/graphene quantum dots and chitosan hydrogel composites, all of which have been exploited due to their contributions as components of a biosensor either for improving the immobilization process or for their electrocatalytic activity towards glucose. This review aims to summarize the evolution of the biosensing aspect of these glucose sensors in terms of the various generations and recent trends based on the use of applied nanostructures for glucose detection in the presence and absence of the enzyme. We describe the history of these biosensors based on commercialized systems, improvements in the understanding of the surface science for enhanced electron transfer, the various sensing platforms developed in the presence of the nanomaterials and their performances.

A modified, thermal atomic layer deposition process was employed for the pulsed chemical vapor deposition growth of vanadium pentoxide films using tetrakis (dimethylamino) vanadium and water as a co-reagent.Depositions were carried out at 350oC for 400 pulsed CVD cycles, and samples were subsequently annealed for 1hour at 400°C in air to form materials with enhanced cycling stability during the continuous lithium-ion intercala­tion/deintercalation processes. The diffusion coefficient was estimated to be 2.04x10-10 and 4.10x10-10 cm2 s-1 for the cathodic and anodic processes, respectively. These values are comparable or lower than those reported in the literature, indicating the capability of Li+ of getting access into the vanadium pentoxide framework at a fast rate. Overall, it presents a specific discharge capacity of 280 mAh g-1, capacity retention of 75 % after 10000 scans, a coulombic efficiency of 100 % for the first scan, dropping to 85 % for the 10000th scan, and specific energy of 523 Wh g-1.

The need for clean and efficient energy storage has become the center of attention due to the eminent global energy crisis and growing ecological concerns. A key component in this effort is the ultra-high performance battery, which will play a major role in the energy industry. To meet the demands in portable electronic devices, electric vehicles, and large-scale energy storage systems, it is necessary to prepare advanced batteries with high safety, fast charge ratios, and discharge capabilities at a low cost. Cathode materials play a significant role in determining the performance of batteries. Among the possible electrode materials is vanadium pentoxide, which will be discussed in this review, due to its low cost and high theoretical capacity. Additionally, aqueous electrolytes, which are environmentally safe, provide an alternative approach compared to organic media for safe, cost-effective, and scalable energy storage. In this review, we will reveal the industrial potential of competitive methods to grow cathodes with excellent stability and enhanced electrochemical performance in aqueous media and lay the foundation for the large-scale production of electrode materials.

We demonstrate the capabilities of the surface pressure-controlled Langmuir-Blodgett method for the deposition of large-area and highly ordered colloidal crystal films made from monodispersed silica particles having diameters of 600 nm onto flexible polymer sheet and highly-curved light bulb and optical fiber cable surfaces. Via the subsequent addition of an appropriate optical adhesive, our processing results in the formation of highly robust films on the various substrates which can be easily handled without introducing damage. Importantly, we demonstrate that due to the highly ordered nature of the particle films and the residual refractive index contrast that is present in the final composite structures, all films retain at least some of the highly desirable anti-reflective and diffractive properties exhibited by analogous films deposited onto flat substrates. This work opens up the possibility of using colloidal crystal films to induce a range of interesting and potentially commercially significant properties on flat and highly-curved, real-sized, shaped device structures.

This paper reports the first-ever presentation of evidence for room-temperature ferroelectric behavior in anatase-phase titanium dioxide (a-TiO2). It is shown that behaviour strongly indicative of ferroelectric behavior is induced in ultra-thin (20nm to 80nm) biaxially-strained epitaxial films of a-TiO2 deposited by liquid injection chemical vapour deposition onto (110) Submitted to neodymium gallium oxide (NGO) substrates. The structural properties of the films were analyzed by x-ray diffraction and high-resolution transmission electron microscopy, which showed significant orthorhombic strain in films. Possible ferroelectric behavior was probed by piezoresponse force microscopy (PFM). The films on NGO showed a switchable dielectric spontaneous polarization, the ability to retain polarization information written into the film using the PFM tip for extended periods (several hours) and at elevated temperatures (up to 100°C) without significant loss, and the disappearance of the polarization at a temperature between 180 and 200°C, indicative of a Curie temperature within this range. This combination of effects is believed to constitute strong experimental evidence for ferroelectric behavior, which has not hitherto been reported in a-TiO2 and opens up the possibility for a range of new devices and materials applications. A model is presented for the effects of large in-plane strains on the crystal structure of anatase which provides a possible explanation for the experimental observations.

Metal oxides like zinc oxide (ZnO) are particularly promising materials to be used in core technologies for the generation and storage of clean energy such as batteries, photovoltaics or solar fuel production and solar water splitting. The deposition of the electrode materials used in these applications should be as cost effective as possible, while maintaining good device characteristics. Here, a simple low-temperature solution-based deposition method is reported that allows for the growth of high surface area, cobalt-doped ZnO nanorod-arrays decorated with cobaltic over-coatings. Control over the visible light absorption and the nature of the cobaltic over-coating (e.g. Co(OH)(2) and/or Co3O4) can be achieved by changing the growth parameters during the one-pot synthesis. Focusing on the evaluation of the underlying growth principles and resulting material properties, the study discusses the crucial role of the organic growth modifier used (monoethanolamine) as a complexing-, growth-directing- and reducing agent. Furthermore, the (solar driven) oxidation of water is taken as an example reaction in order to gain further insight into the functionality of the structures. Accounting for the temperature dependent breakdown of metal-amine complexes, a two-stage growth mechanism is proposed that will allow the optimization of the resulting structures for individual applications, but which could also prove valuable for other metal-oxide/hydroxide material combinations.

We report the development of a dual-enzyme electrochemical biosensor based on microfabricated gold band array electrodes which were first modified by gold foam (Au-foam) in order to dramatically increase the active surface area. The resulting nanostructured Au-foam deposits then served as a highly porous 3D matrix for the electrodeposition of a nanocomposite film consisting of multi walled carbon nanotubes embedded in a chitosan matrix (CS:MWCNT) designed to provide a conducting, biocompatible and chemically versatile surface suitable for the attachment of a wide range of chemically or biologically active agents. Finally, a dual enzyme mixture of glucose oxidase (GOx) and horseradish peroxidase (HRP) was immobilised onto the CS:MWCNT nanocomposite film surface. It is shown that the resulting sensing platform developed demonstrates excellent analytical performance in terms of glucose detection with a sensitivity of 261.8 μA mM-1 cm-2 and a reproducibility standard deviation (RSD) of 3.30% as determined over 7 measurements. Furthermore, long term stability studies showed that the electrodes exhibited an effectively unchanged response to glucose detection after some 45 days. The example of glucose detection presented here illustrates the fact that the particular combination of nanostructured materials employed represents a very flexible platform for the attachment of enzymes or indeed any other bioactive agent and as such may form the basis of the fabrication of a wide range of biosensors. Finally, since the platform used is based on lithographically-deposited gold electrodes on silicon, we note that it is also very suitable for further miniaturisation, mass production and packaging- all of which would serve to reduce production costs.

We have developed a hybrid nanomaterial based on both of carbon quantum dots(CQDs)/gold nanoparticles( AuNPs), such that the cheapness and versatility on the CQDs is directly combined with the inertness and electrochemical activity of the AuNPs to create a new electrochemical biosensor. Here, for the first time, we demonstrate how this interesting materials combination can be applied in the development of an enzymatic biosensor that is easily manufacturable using standard semiconductor processing methods. To demonstrate the potential and performance of the CQDs as an immobilization matrix, glucose oxidase(GOx) enzyme was chosen as a model system. The analytical performance of the developed biosensor was examined using chronoamperometry and the developed CQDs/AuNPs-GOx biosensor exhibited a sensitivity of 47.24 mu A mM(-1) cm(-2) and a detection limit of 17 mu M (S/N = 3) with a linear response to glucose ranging from 0.05 mM to 2.85 mM (R = 0.987). Furthermore, this new biosensor showed a high level of reproducibility and was also shown to be very selective towards glucose in the presence of the possible interference species ascorbic acid, uric acid and acetaminophen. Finally, it is demonstrated that the sensor is also capable of reliably detecting glucose levels in human serum. (c) 2018 Elsevier Ltd. All rights reserved.

A modified, thermal atomic layer deposition process was employed for the pulsed chemical vapour deposition growth of vanadium pentoxide films using tetrakis (dimethylamino) vanadium and water as a co-reagent. Depositions were carried out at 350 °C for 400 pulsed CVD cycles, and samples were subsequently annealed for 1hour at 400 °C in air to form materials with enhanced cycling stability during the continuous lithium-ion intercalation/deintercalation processes. The diffusion coefficients were estimated to be 2.0410-10 and 4.1010-10 cm2 s-1 for the cathodic and anodic processes, respectively. These values are comparable or lower than those reported in the literature, indicating the capability of Li+ of getting access into the vanadium pentoxide framework at a fast rate. Overall, it presents a specific discharge capacity of 280 mA h g-1, capacity retention of 75 % after 10000 scans, a coulombic efficiency of 100 % for the first scan, dropping to 85 % for the 10000th scan, and specific energy of 523 W h g-1.

We demonstrate the successful electrodeposition of Cu nanodendrite foams (CuFoams) onto a series of lithographically formed gold band array electrodes at negative overpotentials in an acidic environment. The nanodendrite foams were deposited onto two different integrated microelectrode arrays fabricated using standard lithographic techniques. Each electrode consisted of 17 gold band electrodes deposited onto a silicon wafer substrate, labeled BA5 (with a width of 5 mu m and a length of 250 mu m) and BA10 (with a width of 10 mu m and a length of 500 mu m). Prior to Cu deposition the gold electrodes were characterized by scanning electron microscopy (SEM) in order to evaluate the morphology of each design and by cyclic voltammetry (CV) in order to investigate their diffusion profiles. After Cu deposition the resulting 3D foam structures were studied using SEM, XPS, and EDX. The CuFoam/Au microelectrodes were then used for the electrocatalytic detection of glucose via oxidation at a potential of +0.45 V vs Ag/AgCl in an alkaline medium. It was found that both types of electrode arrays used showed excellent analytical performance in terms of sensitivity, reproducibility, and stability in comparison with the best performances reported in the literature. In particular, the BA5-CuFoam electrode exhibited an outstanding sensitivity of 10,630 mu A mM(-1) cm(-2) toward glucose with a wide linear range up to 22.55 mM, while the BA10-CuFoam electrode showed a sensitivity of 4,437 mu A mM(-1) cm(-2). The performance of the proposed electrochemical sensor is attributed to a combination of the use of the very high surface area Cu nanodendrite foam and the enhanced radial distribution profile associated with the use of the smaller band microfabricated electrodes. Additionally, both sensors also showed a strong resistance to the poisoning effects of chlorine ions and excellent stability over a period of three months.

The coating of complex three-dimensional structures with ultrathin metal films is of great interest for current technical applications, particularly in microelectronics, as well as for basic research on, for example, photonics or spintronics. While atomic layer deposition (ALD) has become a well-established fabrication method for thin oxide films on such geometries, attempts to develop ALD processes for elemental metal films have met with only mixed success. This can be understood by the lack of suitable precursors for many metals, the difficulty in reducing the metal cations to the metallic state, and the nature of metals as such, in particular their tendency to agglomerate to isolated islands. In this review, we will discuss these three challenges in detail for the example of Cu, for which ALD has been studied extensively due to its importance for microelectronic fabrication processes. Moreover, we give a comprehensive overview over metal ALD, ranging from a short summary of the early research on the ALD of the platinoid metals, which has meanwhile become an established technology, to very recent developments that target the ALD of electropositive metals. Finally, we discuss the most important applications of metal ALD.

The coating of complex three-dimensional structures with ultrathin metal films is of great interest for current technical applications, particularly in microelectronics, as well as for basic research on, for example, photonics or spintronics. While atomic layer deposition (ALD) has become a well-established fabrication method for thin oxide films on such geometries, attempts to develop ALD processes for elemental metal films have met with only mixed success. This can be understood by the lack of suitable precursors for many metals, the difficulty in reducing the metal cations to the metallic state, and the nature of metals as such, in particular their tendency to agglomerate to isolated islands. In this review, we will discuss these three challenges in detail for the example of Cu, for which ALD has been studied extensively due to its importance for microelectronic fabrication processes. Moreover, we give a comprehensive overview over metal ALD, ranging from a short summary of the early research on the ALD of the platinoid metals, which has meanwhile become an established technology, to very recent developments that target the ALD of electropositive metals. Finally, we discuss the most important applications of metal ALD. Published under license by AIP Publishing.

2 Spectroscopic ellipsometry (SE) has been used to measure the full optical response 3 of plasmonic structures. Firstly, the simple case of an anisotropic thin plasmonic layer 4 supported on a transparent substrate is analysed by introducing a quantity named 5 anisotropic surface excess function (ASEF). Such a quantity can be directly extracted 6 from the experiment and simulated using either analytical or numerical methods. Af7 terwards, the formalism has been generalised using a transfer matrix method. In this 8 way effects on the ellipsometric spectra of thick plasmonic films, anisotropic substrates, 9 plasmonic structures grown on top of a multilayer system are described in terms of 10 ∗To whom correspondence should be addressed †Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN) and School of Physics, Trinity College Dublin, Dublin 2 , Ireland ‡Tyndall Institute, Unversity of Cork, IRELAND 1 changes in the effective dielectric function of the system. The analysis developed here 11 has been supported by experimental evidences obtained by measuring the response of 12 anisotropic NP arrays grown at glancing angle. The agreement between theory and 13 experiment is clear, suggesting that SE can be conveniently employed to measure the 14 spectroscopic response of plasmonic structures. It is also demonstrated how the figure 15 of merit of the plasmonic resonances can be greatly improved, with particular measure16 ment configurations, using SE. This can increase the sensitivity of any refractive index 17 based plasmonic sensor. Finally, compared to normal transmission spectroscopies, SE 18 can easily measure the out-of-plane response of the plasmonic systems, providing a 19 much more stringent test for the suitability of certain models to simulate the far field 20 response of a plasmonic system. 21