Discovering the fundamental principles that govern electrochemical reactivity is the key to the design of new materials for a range of scientific applications. Such information can only be obtained from model systems with well-defined elemental reaction sites using state-of-the-art instrumental probes. In this collaborative project we aim to extend the study of electrochemical reactions on model single crystal surfaces in non-aqueous electrolytes. Electrochemistry underpins many current energy applications and plays a crucial role in the development of new energy storage technologies. Advances in all the fields involved in electrochemically based energy technologies will be facilitated by strong synergies between scientific understanding and technological innovation and development. Advances in modern electrochemical surface science offer strong perspectives towards achieving these aims and are central to this application. Indeed detailed in situ characterisation of complex, reactive interfaces is a key area where the tools of electrochemical surface science can meet the challenges of developing technologies. This is particularly true in the case of the lithium-oxygen battery. A greater fundamental understanding of the oxygen cathode interface with respect to the oxygen reduction and oxygen evolution reactions is critical for significant advancement in this area. Electrochemical processes occur at heterogeneous interfaces within a condensed matter environment and are thus more difficult to examine than gas-solid interfaces. Due to the buried nature of the interface, it is inaccessible to most standard surface science techniques that employ strongly adsorbed electron probes to gain surface sensitivity. Study of the interface is restricted to techniques that employ penetrating radiation, such as x-ray and neutron scattering and optical spectroscopy, or imaging techniques, where the probe is brought in close proximity to the solid surface. Development of these relatively new techniques is providing the main methodological driving force for new investigations of the solid/liquid interface. This has been paralleled by the advancements made in synchrotron radiation, where a third generation of light sources is currently operational around the world. This proposal aims to strengthen the collaboration between scientists at the University of Liverpool and Argonne National Laboratory in the study of this complex interface. The collaboration will involve the sharing of equipment, materials and expertise and the training of PhD students in the use of state-of-the-art experimental equipment. It will also involve the use and development of synchrotron radiation techniques for probing the atomic structure at the interface between a solid electrode and a non-aqueous electrolyte.

The coherent oscillations of mobile charge carriers near the surface of good conductors-surface plasmons- have amazing properties. Light can be coupled to these surface plasmons and trapped by them near the interface between a metal and an adjacent material. This leads to the nanoscale confinement of light, impossible by any other means, and a related electromagnetic field enhancement. The associated effects and applications include high sensitivity to the refractive index of surroundings used in biosensors, enhancement of Raman scattering near the metal surfaces used in chemical sensing and detection, enhanced nonlinear optical effects, localised light sources for imaging, and many others. At the same time the influence of the electrons which participate in the formation of surface plasmons on the surroundings of the metal nanostructures is virtually unexplored. Microscopic electron dynamic effects associated with surface plasmons are capable of significantly influencing physical and chemical processes near the metal surface, not (only) as a result of the high electric fields, but also from the transfer of energetic electrons to the adjacent molecules or materials. We propose to develop a comprehensive research programme in order to understand the physics and harness applications associated with such electronic processes, induced by plasmonic excitations, in designer nanostructures. This will open up new paradigms in ultrafast control over nanoscale chemical reactions switchable with light, optically controlled catalysis, optical and electric processes in semiconductor devices induced by plasmonic hot-electrons, as well as nanoscale and ultrafast temperature control, and many other technologies of tomorrow.

United States of America

Resistance is futile: lightbulbs and heaters aside, the majority of electronic components are at their most efficient when their electrical resistance is minimized. In the present climate, with energy sustainability regularly topping the international agenda, reducing the power lost in conducting devices or transmission lines is of worldwide importance. Research into the nature of novel conducting materials is hence vital to secure the global energy future.Superconductivity, the phenomenon of zero electrical resistance which occurs below a critical temperature in certain materials, remains inadequately explained. At present, these critical temperatures are typically very low, less than 140 Kelvin (-133 Celsius), but a more complete understanding of what causes the superconducting state to form could result in the design of materials that display superconductivity at the enhanced temperatures required for mass technological exploitation. Unfortunately, it is the very materials which are most likely to lead us to this end, the so-called unconventional superconductors, that are the least understood. In such materials, the superconducting state appears to be in competition with at least two other phases of matter: magnetism and normal, metallic conductivity. A delicate balance governs which is the dominant phase at low temperatures; the ground-state. By making slight adjustments to the composition of the materials or by applying moderate pressures certain interactions between the electrons in the compound can be strengthened at the expense of others causing the balance to tip in favour of a particular ground-state. The technicalities of how to do this are relatively well-known. What remains to be explained is why it happens, what it is that occurs at the vital tipping point where the superconductivity wins out over the magnetic or the metallic phases - in short, exactly what stabilizes the unconventional superconducting state? It is this question that the proposed project seeks to answer. I will use magnetic fields to explore the ground-states exhibited by three families of unconventional superconductor: the famous cuprate superconductors (whose discovery in the 1980s revolutionized the field of superconductivity and which remain the record-holders for the highest critical temperature); some recently discovered superconductors based on the most magnetic of atoms - iron (the discovery of these new materials in the spring of 2008 came as somewhat of a surprise, magnetism often being thought as competing with superconductivity); and a family of material based on superconducting layers of organic molecules. I propose to measure the strength of the interactions that are responsible for the magnetic and electronic properties of these materials as the systems are pushed, using applied pressure, through the tipping point at which the superconductivity becomes dominant. In particular, the electronic interactions in layered materials like those considered here can only be reliably and completely determined via a technique known as angle-dependent magnetoresistance. This technique remains to be applied to most unconventional superconductors, particularly at elevated pressures, mostly likely because it is experimentally challenging and familiar only to a handful of researchers. However, the rewards of performing such experiments are a far greater insight into what changes in interactions occur at the very edge of the superconducting state. Chasing the mechanism responsible for stabilizing unconventional superconductivity is an ambitious aim, and many traditional experimental techniques have proved inadquate. It is becoming clear, in the light of recent advances in the field, that the route to success lies in subjecting high-quality samples to the most extreme probes available, a combination of high magnetic fields and high applied pressures.

Diamond is the epitome of an extreme material, with un-rivalled multi-functional properties ranging from the thermal and mechanical, through the electrical to the optical. World leading UK research on the synthesis, processing and defect engineering of diamond has reached a pivotal and critical threshold: the promise of diamond enabled innovative technologies is now ripe and for the taking, leading to tremendous technological possibilities. For example, specific placement of defects in diamond paves the way for next-generation quantum computers. Defect engineered nanoparticles results in biocompatible light-emitting particles that can be tracked in the body using powerful microscopes. Interfacing and integrating diamond into electronic devices can solve the biggest problem in electronics today, effective cooling for faster and more reliable device. In photonics too, diamond holds the key to both lasers that are simultaneously more powerful and compact and to single photon sources for secure data transmission. As materials become more advanced, processing must keep pace so we can machine faster with tools that last longer. Only engineered diamond can provide the solution. Training a student to a standard to tackle anyone of these projects, results in a highly multi-disciplinary skilled graduate equipped not just for DST but a wide variety of high performance material applications. Innovation on a timescale suitable to realise commercial opportunities, requires a new breed of graduate, one that can work across disciplines with a skill-set that enables the multi-disciplinary research challenges to be tackled head on. Failure to do so can be expected to lead to slow decline as the innovation is increasingly outsourced and the UK's technological lead eroded. For this reason the academic and industrial community seek to establish a flagship graduate training programme that provides a powerbase for DST training and research activities in the UK, bringing together academics from eight partner universities, with industrial input embedded throughout. Graduates will emerge, trained with expertise across disciplines covering synthesis, material science, modelling, characterisation, engineering, device integration and material processing, photonics, quantum, entrepreneurship etc in addition to transferable skills. Partnership with industry is essential to the vitality of our vision. We have established an Industry Partnership Network (IPN) to help foster and nurture collaborations of mutual interest, and have already secured strategic alliances with sixteen companies and the UK national synchrotron facility, discussions with more are on-going. Our partners have provided funds to support up to twenty three studentships to tackle innovative challenges of interest centred this CDT, demonstrating DST is not a niche area. Their commitment to the CDT, and desire to engage, is motivated by (at least) two factors: (i) their ability to access graduates with the wide-ranging, multi-disciplinary skill sets required to enable the technological opportunities offered by DST, and (ii) their realisation of the tremendous potential impact of high performance materials on societal and technological challenges. This is further confirmed by their readiness to provide presentations on career opportunities showcase facilities and provide research lectures. Essential to the success of the centre is provision of a supportive, interactive, cross-community and cross-disciplinary environment to enable the most effective lines of communications, most efficient training experience and rewarding research projects. The IPN will operate to ensure successful interactions between industry and the CDT and to help develop strategic industry-industry interactions e.g. from the diamond growers to the end users. Cohort integrity during the PhD projects will be maintained via regular online discussion meetings, team building activities and student led conferences.