Concerns about climate change and the extinction of fossil fuels have brought much recent attention to alternative ways of producing energy, but also to strategies to reduce energy consumption. It is estimated that the built environment consumes 30-40% of the primary energy in the world, most of which goes to cooling, heating and lighting. Recent research has demonstrated that it is possible to significantly reduce the energy utilisation in buildings by employing "smart" windows, which are capable of adapting to external weather conditions in a way that minimises the need for heating or air conditioning. A very promising technology to achieve this goal is based on coating glass windows with a very thin film of modified vanadium oxide (VO2). This oxide, which does not conduct electricity at room temperature, is known to become a metallic conductor at temperatures above 68 degrees Celsius. This transition can be tuned to take place at room temperature by introducing some impurity atoms (e.g. tungsten), and it is accompanied by a significant change in the optical properties of the material. Thus, in hot weather, the coating film is metallic and reflects most of the infrared radiation from the Sun, keeping the interior cool, but still allows most visible light to pass. During cooler weather the window coating transforms back to the low-temperature phase, which allows more of the infrared radiation to pass, decreasing the need for internal heating. In this way, large amounts of energy can be saved. I propose here to employ advanced computer simulation techniques to investigate a group of phenomena associated with the design and functioning of VO2-based window coatings. I will first focus on the fundamental and not-yet-resolved design problem for this technology: how to dope the VO2 films in a way that not only the transition temperature is shifted to the required value, but also the colour of the films and the optical properties of the film are acceptable for commercial use. Other important associated phenomena will also be investigated. For example, recent experiments have shown that the introduction of gold nanoparticles allows the modification of the colour of the films, which is important for aesthetic reasons, as tungsten-doped VO2 exhibits a rather unpleasant brown/yellow shade. It has even been suggested that doping with gold nanoparticles can decrease the switching temperature of the film, possibly due to electron transfer to the oxide. I aim to provide a microscopic description of these phenomena. Finally, I also want to understand how the films adhere to the window glass. The adherence of current films is not perfect, which can limit their durability or range of applications. So I want to gain insight into the microscopic factors controlling adhesion, with the hope that this knowledge will lead to more robust and versatile coating technologies. Although modern advances in computer power and theoretical algorithms have made possible the investigation of realistic models of many materials, VO2 belongs to a class of compounds which are particularly challenging for computational modelling. In these materials, which mainly include transition metal and rare earth compounds, the interactions between electrons are so strong that the typical independent-electron approximations employed in solid state calculations do not work well. However, in the last few years powerful and efficient new methods have been developed and implemented in mainstream computer codes, allowing for the first time a realistic modelling of these strongly correlated solids. Using these tools, I will be able to offer a microscopic description of the exciting range of phenomena at the basis of the smart windows coating technology.

This project will involve the investigation of alternative precursors and deposition technologies in order to improve performance and enable next generation transparent conducting oxide (TCO) films to be developed. Indium tin oxide (ITO) is the current TCO of choice for most industrial applications but it has many limitations, such as modest conductivity (2000-4000 S/cm), a relatively low work function and some optical absorption in the blue-green spectral region. In addition, indium is expensive since it is in relatively short supply, which presents a significant challenge for larger-scale production of next generation photovolatic technologies and flat panel displays. It is therefore crucial to develop alternative TCO materials with no indium with improved optical and electrical properties. Alternatives to ITO include doped ZnO (ZnO:Al, ZnO:Ga, ZnO:SnO2) and doped SnO2 (SnO2:Sb, SnO2:F, ZnO-SnO2) and many of these have been investigated in their bulk form. However, studies of some of these materials as thin films is limited and for many of the applications thin films are required. An ideal method for preparing thin fims for large scale applications is chemical vapour deposition (CVD) given that films with good uniformity and compositional control, large area growth and step coverage can be achieved. However, for a successful CVD process, a volatile precursor is necessary which is prefereably a liquid or low metling solid for atmospheric pressure CVD or highly soluble for liquid based (aerosol assisted) CVD. Current precursors to TCO materials, particularly indium and zinc still suffer from chemical instability, poor reproducibility in the growth process and less than favourable vapour pressures and reactivity for film growth. This work aims to develop highly volatile and soluble precursors based on metal ketoiminates. The advantages of using the ketoiminate ligand include: - reactive complexes can be formed in high yield - complexes with a hign vapour pressure can be formed as monomeric species are isolated - thermal stability of the metal complexes can be increased by tuning the groups attached to the nitrogen atoms - the surface reaction between the metal precursor and the surface of the substrate can be enhanced due to the high chemical reactivity of the complexes. TCO materials to be investigated include doped-ZnO and doped-SnO2. We have the ability to lay down thin films using a new combinatorial aerosol-assisted (AA)CVD reactor for solution based and also a combinatorial APCVD reactor to make films of graded composition. This new reactor enables upto 400 different compositions to be made on a single plate in one CVD experiment. This is important as it will enable us to rapidly screen composition space make idealised and optimised compositions for TCO applications. This combined approach will enable us to investigate different combinations and go towards achieving the next generation TCO materials.

Smart thermochromic windows whose insulation properties are tuned by the ambient temperature have been investigated extensively over recent years to improve energy efficiency of commercial and residential buildings. These windows are typically coated with thermochromic materials that exhibit a fully reversible, temperature dependent transition between semiconductor and metallic phases. During hot weather, a smart window passes all or part of the visible radiation incident and rejects the majority of the Sun's near-infrared radiation; thus the need for air conditioning is reduced. During cooler weather, both visible and infrared (IR) radiation is fully transmitted, limiting the need for internal heating. A popular material for such intelligent coatings is Vanadium dioxide (VO2) due to i) the radiation stop-band manifesting in the IR region, ii) the advantage that it can easily be applied to large substrates and iii) the ability to lower its phase transition temperature by doping it with metal compounds, most commonly tungsten. Calculations have shown that a VO2 coating can deliver a 30% reduction in energy consumption of buildings in countries with hot climates such as Italy and Egypt. Nonetheless, the merits of VO2 coatings quickly diminish in colder climates and in places like Helsinki or Moscow they, in fact, deliver a negative energy balance. One very important factor for this performance reversal is the high refractive index that VO2 exhibits in its cold-transparent phase, which results in a large portion of the incident light being reflected - 30%-35% in the visible for a 50 nm thick VO2 film on glass. This figure compares with <4% reflectivity in conventional glass windows, meaning that a thermochromic window is much darker and colder than its plain glass counterpart in the winter, which in turn translates to an actual increase in the energy required for lighting and heating a building. In addition, dirt and stains further degrade the transmission properties of a smart window. In order to overcome the above limitations, moth-eye type structures engineered to exhibit broadband and wide-angle antireflection properties are proposed, for the first time, to substantially improve the currently poor transmission properties of thermochromic smart windows and to pave the way for the commercialization of this technology. Our nanopatterned windows potentially have 72% higher transmission compared to existing thermochromic windows and in addition, they exhibit simultaneous self-cleaning properties without additional processing. This challenging, proof-of-concept, 24-month research project focuses on the fabrication and characterization of smart windows enhanced with moth-eye nanostructures and is divided into two research streams: A) Fabrication and characterization of antireflection and self-cleaning moth-eye nanostructures directly onto glass, appropriate for new high-end window products. B) Development of potentially low-cost thermochromic polymer thin-film to retrofit existing non-smart windows.

Concerns about climate change and the extinction of fossil fuels have brought much recent attention to alternative ways of producing energy, but also to strategies to reduce energy consumption. It is estimated that the built environment consumes 30-40% of the primary energy in the world, most of which goes to cooling, heating and lighting. Recent research has demonstrated that it is possible to significantly reduce the energy utilisation in buildings by employing "smart" windows, which are capable of adapting to external weather conditions in a way that minimises the need for heating or air conditioning. A very promising technology to achieve this goal is based on coating glass windows with a very thin film of modified vanadium oxide (VO2). This oxide, which does not conduct electricity at room temperature, is known to become a metallic conductor at temperatures above 68 degrees Celsius. This transition can be tuned to take place at room temperature by introducing some impurity atoms (e.g. tungsten), and it is accompanied by a significant change in the optical properties of the material. Thus, in hot weather, the coating film is metallic and reflects most of the infrared radiation from the Sun, keeping the interior cool, but still allows most visible light to pass. During cooler weather the window coating transforms back to the low-temperature phase, which allows more of the infrared radiation to pass, decreasing the need for internal heating. In this way, large amounts of energy can be saved. I propose here to employ advanced computer simulation techniques to investigate a group of phenomena associated with the design and functioning of VO2-based window coatings. I will first focus on the fundamental and not-yet-resolved design problem for this technology: how to dope the VO2 films in a way that not only the transition temperature is shifted to the required value, but also the colour of the films and the optical properties of the film are acceptable for commercial use. Other important associated phenomena will also be investigated. For example, recent experiments have shown that the introduction of gold nanoparticles allows the modification of the colour of the films, which is important for aesthetic reasons, as tungsten-doped VO2 exhibits a rather unpleasant brown/yellow shade. It has even been suggested that doping with gold nanoparticles can decrease the switching temperature of the film, possibly due to electron transfer to the oxide. I aim to provide a microscopic description of these phenomena. Finally, I also want to understand how the films adhere to the window glass. The adherence of current films is not perfect, which can limit their durability or range of applications. So I want to gain insight into the microscopic factors controlling adhesion, with the hope that this knowledge will lead to more robust and versatile coating technologies. Although modern advances in computer power and theoretical algorithms have made possible the investigation of realistic models of many materials, VO2 belongs to a class of compounds which are particularly challenging for computational modelling. In these materials, which mainly include transition metal and rare earth compounds, the interactions between electrons are so strong that the typical independent-electron approximations employed in solid state calculations do not work well. However, in the last few years powerful and efficient new methods have been developed and implemented in mainstream computer codes, allowing for the first time a realistic modelling of these strongly correlated solids. Using these tools, I will be able to offer a microscopic description of the exciting range of phenomena at the basis of the smart windows coating technology.

New optoelectronically and photonically active materials - such as organic semiconductors and nanoparticles - are bringing to market new technologies and products such as organic light-emitting diodes (OLEDs) and new phosphors (as used in QD TVs and LED white lighting). Our understanding of the fundamental properties of these materials as well as the rate of design of new materials is accelerating. Of particular interest is a new generation of systems combining organic semiconductors with inorganic nanoparticles. These hybrid blends or nanocomposites hold great promise as a platform technology for high-efficiency low-cost solar energy harvesting devices, photodetectors and novel LEDs for displays, communications and chemical diagnostics. A scalable manufacturing process for these materials will rely on solution processing of an ink comprising the organic semiconductor, the nanoparticles and a suitable solvent to produce a functional film or coating. However, the components of these organic-nanoparticle blends have a strong tendency to aggregate and phase separate during solution processing, due to a mismatch of their size, shape and surface energies1. This severely compromises device performance and to date has ruled out the manufacture of these systems via large-area-compatible solution manufacturing techniques such as bar-coating, slot-die coating or inkjet printing. Our proposed methodology will overcome these problems, demonstrating routes by which the two active components spontaneously self-assemble during deposition and subsequent solvent evaporation to yield a nanocomposite with a precise morphology and structure over the hierarchy of length scales described above. Thus, our proposal directly tackles the challenge of achieving the precision manufacture at scale of functional nanocomposites. We seek to develop new molecular engineering methodologies providing a toolkit of manufacturing approaches enabling precise control over a hierarchy of length scales. This will create manufacturing routes a new generation of optoelectronically and photonically active coatings and films based on organic-nanoparticle blends, accelerating the translation of fast-moving developments in the physics and chemistry of these hybrid materials into economic benefit for the UK and benefits to society world-wide.