Functional films underpin many electronic and opto-electronic devices, including flat panel displays, OLED's, image sensors, thin film photovoltaic solar cells, etc. Of particular importance to these devices are transparent conductive oxide (TCO) films, such as indium tin oxide (ITO) and aluminium-doped zinc oxide (ZAO). The UK market for functional films is expected to rise to 23.4B by 2010. Further substantial gains in productivity would be made, and new markets opened up, if the devices could be deposited directly onto polymeric web in very large throughput reel-to-reel coaters. However, the deposition of TCO films onto webs poses many significant technological challenges. In comparison to glass, polymeric webs are relatively rough, tend to outgas significantly and are thermally sensitive. The latter point particularly poses a problem, because it is generally necessary to perform a post-deposition annealing process (typically at 500 degC) in order to optimise the optical and electrical properties of TCO materials.One potential solution to this problem is to deposit coatings using the newly developed technique of high powered impulse magnetron sputtering (HIPIMS). This process involves the application of very large power pulses to magnetron sputter cathodes for short periods of time. The peak pulse power can be in the megawatt range and the pulse duration is typically of the order of 80-160 micro seconds, at repetition rates in the range of 10s to 100s of Hz. Initial studies of the HIPIMS (also referred to as high power pulsed magnetron sputtering / HPPMS) system have shown that this intense pulse creates a high degree of ionization (up to 70% for titanium) of the sputtered species with this technique (in contrast to conventional magnetron sputtering, where usually less than 1% of the sputtered material is ionized).The degree of ionization of the sputtered species in HIPIMS is comparable to that produced in cathodic arc discharges; however, with HIPIMS macroparticles are not normally produced. Another important consideration is that, due to the very low duty cycles (~1%) and long off times, the total heat load to the substrate can be very significantly (5-10 times) lower than in conventional DC and pulsed DC sputtering. Thus, the potential for HIPIMS is to harness the high degree of ionization to produce films with significantly improved properties, whilst maintaining a suitably low (sub-150 degC) substrate bulk temperature, allowing a diverse range of substrate materials to be coated. The introduction of HIPIMS technology, therefore, has the potential to provide a step-change in the performance of functional films, such as TCO's, deposited onto polymeric webs. This project will offer the first opportunity to study this new, complex deposition process in detail in both a development-scale system at MMU and an industrial pilot scale reel-to-reel coater at Oxford University. An additional key element of the project will be a detailed study of the nature of the discharge. Plasma characteristics such as the spatial and temporal evolution of the concentrations and temperatures of the species and their power loading of the substrate will be determined using an array of time-resolved diagnostic tools and well developed optical imaging techniques. The ability to deposit fully dense TCO coatings with optimised properties onto flexible substrates would be a major breakthrough and would represent a significant advancement in web coating technology.

Material degradation is a primary concern to every material scientist and engineer, not only does degradation lead to failure, but results in the need for repair - a very costly endeavour. In this perspective, it is of interest to develop self-healing materials that will make maintenance redundant. As opposed to inorganic semiconductors, organic semiconducting materials are soft, which makes them ideal to be used in flexible and stretchable electronic devices, which can be directly applied to the human skin. Wearable electronics, however, are particularly prone to mechanical damage and fatigue, which is why it is paramount to develop more robust materials, like self-healable semiconductors. This fellowship will, for the first time, make it possible to synthesise intrinsic self-healing organic semiconductors and incorporate them into fully flexible, stretchable and wearable electronic devices, respectively bionic skin, to measure biological metabolites associated with diabetes (glucose), fatigue (lactate) and stress (cortisol). The electric charges will be transported via the conjugated polymer backbone, while additional supramolecular functionalities (i.e. non-binding interactions) will be incorporated into the chemical structure to ensure self-healing via the formation of dynamic bonds. The study of the new self-healing polymers will then be extended to other dynamically bonding functional groups to evaluate which chemistry is best suited for organic semiconductors. Subsequent steps will focus on the self-healing dynamics and rates, and the incorporation of the new materials into flexible electronic prototype devices. The realisation of healable organic semiconductors, for the first time, will allow the fabrication of lightweight, -wearable sensors directly applied to the human skin. This will make it possible to continuously monitor medically relevant body functions and present a significant step forward in the development of affordable biological sensors and continuous patient monitoring, ultimately enhancing medical diagnostics and opening-up new treatment possibilities.

The proposal seeks funds to renew and refresh the Centre for Doctoral Training in Formulation Engineering based in Chemical Engineering at Birmingham. The Centre was first funded by EPSRC in 2001, and was renewed in 2008. In 2011, on its 10th anniversary, the Centre received one of the Diamond Jubilee Queen's Anniversary Prizes, for 'new technologies and leadership in formulation engineering in support of UK manufacturing'. The scheme is an Engineeering Doctoral Centre; students are embedded in their sponsoring company and carry out industry-focused research. Formulation Engineering is the study of the manufacture of products that are structured at the micro-scale, and whose properties depend on this structure. In this it differs from conventional chemical engineering. Examples include foods, home and personal care products, catalysts, ceramics and agrichemicals. In all of these material formulation and microstructure control the physical and chemical properties that are essential to its function. The structure determines how molecules are delivered or perceived - for example, in foods delivery is of flavour molecules to the mouth and nose, and of nutritional benefit to the GI tract, whilst in home and personal care delivery is to skin or to clothes to be cleaned, and in catalysis it is delivery of molecules to and from the active site. Different industry sectors are thus underpinned by the same engineering science. We have built partnerships with a series of companies each of whom is world-class in its own field, such as P&G, Kraft/Mondelez, Unilever, Johnson Matthey, Imerys, Pepsico and Rolls Royce, each of which has written letters of support that confirm the value of the programme and that they will continue to support the EngD. Research Engineers work within their sponsoring companies and return to the University for training courses that develop the concepts of formulation engineering as well as teaching personal and management skills; a three day conference is held every year at which staff from the different companies interact and hear presentations on all of the projects. Outputs from the Centre have been published in high-impact journals and conferences, IP agreements are in place with each sponsoring company to ensure both commercial confidentiality and that key aspects of the work are published. Currently there are 50 ongoing projects, and of the Centre's graduates, all are employed and more than 85% have found employment in formulation companies. EPSRC funds are requested to support 8 projects/year for 5 years, together with the salary of the Deputy Director who works to link the University, the sponsors and the researchers and is critical to ensure that the projects run efficiently and the cohorts interact well. Two projects/year will be funded by the University (which will also support a lecturer, total >£1 million over the life of the programme) and through other sources such as the 1851 Exhibition fund, which is currently funding 3 projects. EPSRC funding will leverage at least £3 million of direct industry contributions and £8 million of in-kind support, as noted in the supporting letters. EPSRC funding of £4,155,480 will enable a programme with total costs of more than £17 million to operate, an EPSRC contribution of 24% to the whole programme.

Functional films underpin many electronic and opto-electronic devices, including flat panel displays, OLED's, image sensors, thin film photovoltaic solar cells, etc. Of particular importance to these devices are transparent conductive oxide (TCO) films, such as indium tin oxide (ITO) and aluminium-doped zinc oxide (ZAO). The UK market for functional films is expected to rise to 23.4B by 2010. Further substantial gains in productivity would be made, and new markets opened up, if the devices could be deposited directly onto polymeric web in very large throughput reel-to-reel coaters. However, the deposition of TCO films onto webs poses many significant technological challenges. In comparison to glass, polymeric webs are relatively rough, tend to outgas significantly and are thermally sensitive. The latter point particularly poses a problem, because it is generally necessary to perform a post-deposition annealing process (typically at 500 degC) in order to optimise the optical and electrical properties of TCO materials.One potential solution to this problem is to deposit coatings using the newly developed technique of high powered impulse magnetron sputtering (HIPIMS). This process involves the application of very large power pulses to magnetron sputter cathodes for short periods of time. The peak pulse power can be in the megawatt range and the pulse duration is typically of the order of 80-160 micro seconds, at repetition rates in the range of 10s to 100s of Hz. Initial studies of the HIPIMS (also referred to as high power pulsed magnetron sputtering / HPPMS) system have shown that this intense pulse creates a high degree of ionization (up to 70% for titanium) of the sputtered species with this technique (in contrast to conventional magnetron sputtering, where usually less than 1% of the sputtered material is ionized).The degree of ionization of the sputtered species in HIPIMS is comparable to that produced in cathodic arc discharges; however, with HIPIMS macroparticles are not normally produced. Another important consideration is that, due to the very low duty cycles (~1%) and long off times, the total heat load to the substrate can be very significantly (5-10 times) lower than in conventional DC and pulsed DC sputtering. Thus, the potential for HIPIMS is to harness the high degree of ionization to produce films with significantly improved properties, whilst maintaining a suitably low (sub-150 degC) substrate bulk temperature, allowing a diverse range of substrate materials to be coated. The introduction of HIPIMS technology, therefore, has the potential to provide a step-change in the performance of functional films, such as TCO's, deposited onto polymeric webs. This project will offer the first opportunity to study this new, complex deposition process in detail in both a development-scale system at MMU and an industrial pilot scale reel-to-reel coater at Oxford University. An additional key element of the project will be a detailed study of the nature of the discharge. Plasma characteristics such as the spatial and temporal evolution of the concentrations and temperatures of the species and their power loading of the substrate will be determined using an array of time-resolved diagnostic tools and well developed optical imaging techniques. The ability to deposit fully dense TCO coatings with optimised properties onto flexible substrates would be a major breakthrough and would represent a significant advancement in web coating technology.

We propose to mitigate the transmission of COVID-19 between humans by development of antiviral formulated products. It will be delivered via additives in domestic formulated products, e.g. spray or aerosol, or integrated with current manufacturing processes, forming an invisible and long-lasting film of sub-micron thickness. Unlike disinfectants, formulations will be designed to both capture the aerosol droplets and inactivate the virus. Our first priority is to establish a mechanistic understanding of the interactions between aerosol droplets (or pure virus particles) and surfaces, which will inform possible antiviral mechanisms while providing a set of fundamental and coherent design principles for antiviral surfaces. Two technology platforms will be pursued to leverage the expertise and capability of our industrial partners. Polymer additives with controlled chemistry and molecular architecture will be explored to generate molecular films that facilitate disruption of aerosolised droplets and which may rupture the viral envelope or interfere adversely with key viral proteins and or genetic material. Proposed nanocellulose additives will confer additional benefits in terms of providing a porous structure designed to wick and absorb any protective mucus present. In parallel, hybrid polymer technology will be developed, employing reactive oxygen-producing copper nanoparticles coupled with flavin dyes that produce singlet oxygen species known to deactivate viruses when irradiated with light of the appropriate wavelength. Upon satisfactory antiviral testing results, promising design/formulation will be recommended based on their processability, suitability for end-applications, and environmental impact. Industrial partners with substantial experience in formulation will carry out pilot-scale production and full- scale manufacturing subsequently.