Investigation of interfacial charging and discharging in double-layer pentacene-based metal-insulator-metal device with polyterpenol blocking layer using electric field induced second harmonic generation

Time-resolved electric field induced second harmonic generation technique was used to probe the carrier transients within double-layer pentacene-based MIM devices. Polyterpenol thin films fabricated from non-synthetic environmentally sustainable source were used as a blocking layer to assist in visualisation of single-species carrier transportation during charging and discharging under different bias conditions. Results demonstrated that carrier transients were comprised of charging on electrodes, followed by carrier injection and charging of the interface. Polyterpenol was demonstrated to be a sound blocking material and can therefore be effectively used for probing of double-layer devices using EFISHG.

Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.

Increasing attractiveness of high-end products

An important decision brand managers have to make when positioning their products in a retail setting is to whether price new line extensions at parity or let products vary in the price/quality spectrum. Despite the growing interest in vertical line extension issues, there has been little research investigating how product-line length affects extension favorability. Therefore, this paper investigates the framing effect that a product line price structure has on consumer judgments of vertical extensions and, in particular, of upscale extensions. A basic proposition of this research is that the parent brand price range affects the perceived or psychological distance between extension and parent brand, influencing extension favorability ratings. In two experiments, it is shown that positioning an upscale extension in the context of a wide product-line will lead to higher consistency perceptions between the parent brand and a new upscale extension than an equivalent upscale extension positioned in the context of a narrow parent brand product-line.

The interaction of quantum dots with plasmons supported by metal waveguides

Plasmonics is a recently emerged technology that enables the compression of electromagnetic waves into miniscule metallic structures, thus enabling the focusing and routing of light on the nanoscale. Plasmonic waveguides can be used to miniaturise the size of integrated chip circuits while increasing the data transmission speed. Plasmonic waveguides are used to route the plasmons around a circuit and are a major focus of this thesis. Also, plasmons are highly sensitive to the surrounding dielectric environment. Using this property we have experimentally realised a refractive index sensor to detect refractive index change in solutions.

Superhydrophobic fabrics for oil-water separation based on the metal organic charge transfer complex CuTCNAQ

This work reports on the fabrication of a superhydrophobic nylon textile based on the organic charge transfer complex CuTCNAQ (TCNAQ = 11,11,12,12-tetracyanoanthraquinodimethane). The nylon fabric that is metallized with copper undergoes a spontaneous chemical reaction with TCNAQ dissolved in acetonitrile to form nanorods of CuTCNAQ that are intertwined over the entire surface of the fabric. This creates the necessary micro and nanoscale roughness that is required for the Cassie-Baxter state thereby achieving a superhydrophobic/superoleophilic surface without the need for a fluorinated surface. The material is characterised with SEM, FT-IR and XPS spectroscopy and investigated for its ability to separate oil and water in two modes, namely under gravity and as an absorbent. It is found that the fabric can separate dichloromethane, olive oil and crude oil from water and in fact reduce the water content of the oil during the separation process. The fabric is reusable and tolerant to conditions such as seawater, hydrochloric acid and extensive time periods on the shelf. Given that CuTCNAQ is a copper based semiconductor may also open up the possibility of other applications in areas such as photocatalysis and antibacterial applications.

Taxonomy of factors which influence heavy metal build-up on urban road surfaces

Heavy metals build-up on urban road surfaces is a complex process and influenced by a diverse range of factors. Although numerous research studies have been conducted in the area of heavy metals build-up, limited research has been undertaken to rank these factors in terms of their influence on the build-up process. This results in limitations in the identification of the most critical factor/s for accurately estimating heavy metal loads and for designing effective stormwater treatment measures. The research study undertook an in-depth analysis of the factors which influence heavy metals build-up based on data generated from a number of different geographical locations around the world. Traffic volume was found to be the highest ranked factor in terms of influencing heavy metals build-up while land use was ranked the second. Proximity to arterial roads, antecedent dry days and road surface roughness has a relatively lower ranking. Furthermore, the study outcomes advances the conceptual understanding of heavy metals build-up based on the finding that with increasing traffic volume, total heavy metal build-up load increases while the variability decreases. The outcomes from this research study are expected to contribute to more accurate estimation of heavy metals build-up loads leading to more effective stormwater treatment design.

Influence of uncertainty inherent to heavy metal build-up and wash-off on stormwater quality

Uncertainty inherent to heavy metal build-up and wash-off stems from process variability. This results in inaccurate interpretation of stormwater quality model predictions. The research study has characterised the variability in heavy metal build-up and wash-off processes based on the temporal variations in particle-bound heavy metals commonly found on urban roads. The study outcomes found that the distribution of Al, Cr, Mn, Fe, Ni, Cu, Zn, Cd and Pb were consistent over particle size fractions <150µm and >150µm, with most metals concentrated in the particle size fraction <150µm. When build-up and wash-off are considered as independent processes, the temporal variations in these processes in relation to the heavy metals load are consistent with variations in the particulate load. However, the temporal variations in the load in build-up and wash-off of heavy metals and particulates are not consistent for consecutive build-up and wash-off events that occur on a continuous timeline. These inconsistencies are attributed to interactions between heavy metals and particulates <150µm and >150µm, which are influenced by particle characteristics such as organic matter content. The behavioural variability of particles determines the variations in the heavy metals load entrained in stormwater runoff. Accordingly, the variability in build-up and wash-off of particle-bound pollutants needs to be characterised in the description of pollutant attachment to particulates in stormwater quality modelling. This will ensure the accounting of process uncertainty, and thereby enhancing the interpretation of the outcomes derived from modelling studies.

Probing the mechanism of benzaldehyde reduction to chiral hydrobenzoin on the CNT surface under near-UV light irradiation

Metal-free CNTs exhibit high activity (conversion rate 99.6%, 6 h) towards the synthesis of chiral hydrobenzoin from benzaldehyde under near-UV light irradiation (320–400 nm). The CNT structure before and after the reaction, the interaction between the molecule and the CNT surface, the intermediate products, the substitution effect and the influence of light on the reaction were examined using various techniques. A photo-excited conduction electron transfer (PECET) mechanism for the photocatalytic reduction using CNTs has been proposed. This finding provides a green photocatalytic route for the production of hydrobenzoin and highlights a potential photocatalytic application of CNTs.

Thin nanoporous metal-insulator-metal membranes

Insulating nanoporous materials are promising platforms for soft-ionizing membranes; however, improvement in fabrication processes and the quality and high breakdown resistance of the thin insulator layers are needed for high integration and performance. Here, scalable fabrication of highly porous, thin, silicon dioxide membranes with controlled thickness is demonstrated using plasma-enhanced chemical-vapor-deposition. The fabricated membranes exhibit good insulating properties with a breakdown voltage of 1 × 107 V/cm. Our calculations suggest that the average electric field inside a nanopore of the membranes can be as high as 1 × 106 V/cm; sufficient for ionization of wide range of molecules. These metal–insulator–metal nanoporous arrays are promising for applications such soft ionizing membranes for mass spectroscopy.

Metal nanoparticle photocatalysts: Emerging processes for green organic synthesis

Metal nanoparticle photocatalysts have attracted recent interest due to their strong absorption of visible and ultraviolet light. The energy absorbed by the metal conduction electrons and the intense electric fields in close proximity, created by the localized surface plasmon resonance effect, makes the crucial contribution of activating the molecules on the metal nanoparticles which facilitates chemical transformation. There are now many examples of successful reactions catalyzed by supported nanoparticles of pure metals and of metal alloys driven by light at ambient or moderate temperatures. These examples demonstrate these materials are a novel group of efficient photocatalysts for converting solar energy to chemical energy and that the mechanisms are distinct from those of semiconductor photocatalysts. We present here an overview of recent research on direct photocatalysis of supported metal nanoparticles for organic synthesis under light irradiation and discuss the significant reaction mechanisms that occur through light irradiation.

Social and environmental reporting practices of organisations operating in, or sourcing products from, a developing country : evidence from Bangladesh

This research consists of a broad study in three parts of the social and environmental reporting practices of organisations operating in or sourcing products from a developing country, in this case Bangladesh. The first part of this study explores the social and environmental disclosure practices of the Bangladesh Garment Manufacturers and Exporters Association (BGMEA), the body responsible for organising the activities of 4,200 entities involved in the export of garments from Bangladesh. By way of interview, this part documents the opinions of numerous senior executives from the BGMEA with regard to any changes in the degree of social and environmental pressures since 1985. Utilising a complementary theoretical perspective that includes legitimacy theory, stakeholder theory and institutional theory this part then performs an analysis of the BGMEA's annual reports (1987-2005), t o explore the link between the perceived pressures and changes entailed therein and the social and environmental disclosure practices of the BGMEA across the period of analysis. The results show that the disclosure practices of BGMEA appear to be directly driven by the changing expectations of multinational buying companies- the group deemed to be the most powerful stakeholder group. This section is the first known study to interview managers from a large organisation in a developing country about shifting stakeholder expectations and then to link these changing expectations to annual report disclosures across an extended period of analysis. The findings then directly lead to the second major part of this thesis which investigates the social and environmental disclosure practices of two major multinational buying companies: Nike and H&M. Adopting a joint consideration of legitimacy theory and media agenda setting theory, this second part investigates the linkage between negative media attention and positive corporate social and environmental disclosures over a 19 year period. The results support the view that for those industry-related social and environmental issues that attract the greatest amount of negative media attention, these companies react by providing positive social and environmental disclosures. The results were particularly significant in relation to labour practices in developing countries-the issue that attracts the greatest amount of negative media attention for the companies in question. While the second part demonstrates that the media influences particular disclosure practices, the third part of the thesis shows what drives the media. Based on the speculation provided in the second part, the third part tests the proposition that the media is an important ally of NGOs in their quest to influence change in corporate accountabilities. Through the use of interviews, the results of this part of the study provide evidence to support previously untested perspectives about NGOs' utilisation of the m edia. The results reveal that NGOs use the media because the media is responsible for creating real changes in the operations and disclosure policies of organisations sourcing products from Bangladesh. The various pressures impacting the activities of organisations operating in or sourcing products from developing countries constitutes a fascinating area of investigation, and it is hoped that this study will motivate further research in this area.

Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets

Two-dimensional (2D) transition metal oxide systems present exotic electronic properties and high specific surface areas, and also demonstrate promising applications ranging from electronics to energy storage. Yet, in contrast to other types of nanostructures, the question as to whether we could assemble 2D nanomaterials with an atomic thickness from molecules in a general way, which may give them some interesting properties such as those of graphene, still remains unresolved. Herein, we report a generalized and fundamental approach to molecular self-assembly synthesis of ultrathin 2D nanosheets of transition metal oxides by rationally employing lamellar reverse micelles. It is worth emphasizing that the synthesized crystallized ultrathin transition metal oxide nanosheets possess confined thickness, high specific surface area and chemically reactive facets, so that they could have promising applications in nanostructured electronics, photonics, sensors, and energy conversion and storage devices.

3D hierarchical rutile TiO2 and metal-free organic sensitizer producing dye-sensitized solar cells 8.6% conversion efficiency

Three-dimensional (3D) hierarchical nanoscale architectures comprised of building blocks, with specifically engineered morphologies, are expected to play important roles in the fabrication of 'next generation' microelectronic and optoelectronic devices due to their high surface-to-volume ratio as well as opto-electronic properties. Herein, a series of well-defined 3D hierarchical rutile TiO2 architectures (HRT) were successfully prepared using a facile hydrothermal method without any surfactant or template, simply by changing the concentration of hydrochloric acid used in the synthesis. The production of these materials provides, to the best of our knowledge, the first identified example of a ledgewise growth mechanism in a rutile TiO2 structure. Also for the first time, a Dye-sensitized Solar Cell (DSC) combining a HRT is reported in conjunction with a high-extinction-coefficient metal-free organic sensitizer (D149), achieving a conversion efficiency of 5.5%, which is superior to ones employing P25 (4.5%), comparable to state-of-the-art commercial transparent titania anatase paste (5.8%). Further to this, an overall conversion efficiency 8.6% was achieved when HRT was used as the light scattering layer, a considerable improvement over the commercial transparent/reflector titania anatase paste (7.6%), a significantly smaller gap in performance than has been seen previously.

Liberty relighting, 20 years later

Recognized around the world as a powerful beacon for freedom, hope, and opportunity, the Statue of Liberty's light is not just metaphorical: her dramatic illumination is a perfect example of American ingenuity and engineering. Since the statue's installation in New York Harbor in 1886, lighting engineers and designers had struggled to illuminate the 150-foot copper-clad monument in a manner becoming an American icon. It took the thoughtful and creative approach of Howard Brandston-a legend in his own right-to solve this lighting challenge. In 1984, the designer was asked to give the statue a much-needed lighting makeover in preparation for its centennial. In order to avoid the shortcomings of previous attempts, he studied the monument from every angle and in all lighting conditions, discovering that it looked best in the light of dawn. Brandston determined that he would need 'one lamp to mimic the morning sun and one lamp to mimic the morning sky.' Learning that no existing lamps could simulate these conditions, Brandston partnered with General Electric to develop two new metal halide products. With only a short time for R&D, a team of engineers at GE's Nela Park laboratories assembled a 'top secret' testing room dedicated to the Statue of Liberty project. After nearly two years of work to perfect the new lamps, the 'dawn's early light' effect was finally achieved just days before the centennial celebrations were to take place in 1986. 'It was truly a labor of love,' he recalls.

Consumer’s comparison between local and imported organic products: A hedonic analysis of the Japanese table wine market

Although hundreds of thousands of organic products are traded on a daily basis, it is less known how imported organic products are evaluated by consumers in an importing country. The paper analyzes Japanese wine point of sale (POS) data to examine whether consumers differentiate between local and imported organic products. The results of our hedonic analyses show that the premium for imported organic red (white) wines is about 42.996 % (8.872 %) while that for domestic red (white) organic wines is about 6.440 % (1.214 %), implying that Japanese consumers pay higher premiums for imported organic agricultural products than for those produced in Japan.