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.

Australian feature films and distribution: Industry or cottage industry?

Feature films remain critical flagships to any national film industry. Australian feature films can be highly commercial endeavours that also perform symbolic functions by embodying the national imaginary in big screen based sound and imagery. They conduct a dialogue with domestic audiences as well as showcase key aspects of Australia in the global film festival circuit. As the pre-eminent filmmaking form, feature films also serve as important launchpads for the careers of many Australian writers, directors, actors and technical crew. In the wake of over a decade of diminished share of local box office obtained by Australian feature films, Australian Feature Films and Distribution: Industry or cottage industry, examines issues in the production sector affecting the performance of Australian feature films and some responses by the central funding and support screen agency, Screen Australia.

Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.

A novel ionic diffusion strategy to fabricate high-performance anode-supported solid oxide fuel cells (SOFCs) with proton-conducting Y-doped BaZrO3 films

A stable Y-doped BaZrO3 electrolyte film, which showed a good performance in proton-conducting SOFCs, was successfully fabricated using a novel ionic diffusion strategy.

Sinteractive anodic powders improve densification and electrochemical properties of BaZr0.8Y0.2O3-δ electrolyte films for anode-supported solid oxide fuel cells

The difficult sintering of BaZr0.8Y0.2O 3-δ (BZY20) powders makes the fabrication of anode-supported BZY20 electrolyte films complex. Dense BZY20 membranes were successfully fabricated on anode substrates made of sinteractive NiO-BZY20 powders, prepared by a combustion method. With respect to traditional anode substrates made of powders prepared by mechanical mixing, the anode substrates made of the wet-chemically synthesized composite NiO-BZY20 powders significantly promoted the densification of BZY20 membranes: dense BZY20 films were obtained after co-pressing and co-firing at 1300 °C, a much lower temperature than those usually needed for densifying BZY20 membranes. Improved electrochemical performance was also observed: the supported BZY20 films maintained a high proton conductivity, up to 5.4 × 10-3 S cm-1 at 700 °C. Moreover, an anode-supported fuel cell with a 30 m thick BZY20 electrolyte film fabricated at 1400 °C on the anode made of the wet-chemically synthesized NiO-BZY20 powder showed a peak power density of 172 mW cm-2 at 700 °C, using La0.6Sr0.4Co 0.2Fe0.8O3-δ-BaZr0.7Y 0.2Pr0.1O3-δ as the cathode material, with a remarkable performance for proton-conducting solid oxide fuel cell (SOFC) applications.

The effect of pressure and W-doping on the properties of ZnO thin films for NO2 gas sensing

Pure and W-doped ZnO thin films were obtained using magnetron sputtering at working pressures of 0.4 Pa and 1.33 Pa. The films were deposited on glass and alumina substrates at room temperature and subsequently annealed at 400oC for 1 hour in air. The effects of pressure and W-doping on the structure, chemical, optical and electronic properties of the ZnO films for gas sensing were examined. From AFM, the doped film deposited at higher pressure (1.33 Pa) has spiky morphology with much lower grain density and porosity compared to the doped film deposited at 0.4 Pa. The average gain size and roughness of the annealed films were estimated to be 65 nm and 2.2 nm, respectively with slightly larger grain size and roughness appeared in the doped films. From XPS the films deposited at 1.33 Pa favored the formation of adsorbed oxygen on the film surface and this has been more pronounced in the doped film which created active sites for OH adsorption. As a consequence the W-doped film deposited at 1.33 Pa was found to have lower oxidation state of W (35.1 eV) than the doped film deposited at 0.4 Pa (35.9 eV). Raman spectra indicated that doping modified the properties of the ZnO film and induced free-carrier defects. The transmittance of the samples also reveals an enhanced free-carrier density in the W-doped films. The refractive index of the pure film was also found to increase from 1.7 to 2.2 after W-doping whereas the optical band gap only slightly increased. The W-doped ZnO film deposited at 0.4 Pa appeared to have favorable properties for enhanced gas sensing. This film showed significantly higher sensing performance towards 5-10 ppm NO2 at lower operating temperature of 150oC most dominantly due to increased free-carrier defects achieved by W-doping.

Fabrication of Fe-doped WO3 films for NO2 sensing at lower operating temperature

Fe-doped tungsten oxide thin films with different concentrations (0 to 2.6 at%) were synthesized on glass and alumina substrates at room temperature using DC reactive sputtering and subsequently annealed at 300oC for 1 hour in air. The alumina substrate has pre-printed interdigitated Pt-electrodes for gas sensing measurements. The effects of Fe-doping on the film structure and morphology, electronic and optical properties for gas sensing were investigated. The grain size of the different films on the alumina and Pt regions of the substrate vary only slightly between 43-57 nm with median size of about 50 nm. Raman spectra showed that the integrated intensity of W=O to O–W–O bands increases with increasing Fe concentrations and this indicated an increase in the number of defects. From XPS the different concentrations of the Fe-doped films were 0.03 at%, 1.33 at% and 2.6 at%. All the films deposited on glass substrate have shown similar visible transmittance (about 70%) but the optical band gap of the pure film decreased form 3.30 eV to 3.15 eV after doping with 2.6 at% Fe. The Fe-doped WO3 film with the highest Fe concentration (2.6 at% Fe) has shown an enhanced gas sensing properties to NO2 at relatively lower operating temperature (150oC) and this can be attributed to the decrease in the optical band gap and an increase in the number of defects compared to the pure WO3 film.

Synergistic crystal facet engineering and structural control of WO3 films exhibiting unprecedented photoelectrochemical performance

WO3 nanoplate arrays with (002) oriented facets grown on fluorine doped SnO2 (FTO) glass substrates are tailored by tuning the precursor solution via a facile hydrothermal method. A 2-step hydrothermal method leads to the preferential growth of WO3 film with enriched (002) facets, which exhibits extraordinary photoelectrochemical (PEC) performance with a remarkable photocurrent density of 3.7 mA cm–2 at 1.23 V vs. revisable hydrogen electrode (RHE) under AM 1.5 G illumination without the use of any cocatalyst, corresponding to ~93% of the theoretical photocurrent of WO3. Density functional theory (DFT) calculations together with experimental studies reveal that the enhanced photocatalytic activity and better photo-stability of the WO3 films are attributed to the synergistic effect of highly reactive (002) facet and nanoplate structure which facilitates the photo–induced charge carrier separation and suppresses the formation of peroxo-species. Without the use of oxygen evolution cocatalysts, the excellent PEC performance, demonstrated in this work, by simply tuning crystal facets and nanostructure of pristine WO3 films may open up new opportunities in designing high performance photoanodes for PEC water splitting.