Organic molecular monolayers at surfaces often constitute the central working component in nanotechnologies such as sensors, molecular electronics, smart coatings, organic solar cells, catalysts, medical devices, etc. A central challenge in the field is to achieve controlled creation of desired 2D molecular architectures at surfaces. Within this context, the past decade has witnessed a real and significant step-change in the 'bottom-up' self-organisation of 2D molecular assemblies at surfaces. The enormous variety and abundance of molecular structures formed via self-oeganisation has now critically tipped the argument strongly in favour of a 'bottom-up' construction strategy, which harnesses two powerful attributes of nanometer-precision (inaccessible to top-down methods) and highly parallel fabrication (impossible with atomic/molecular manipulation). Thus, bottom-up molecular assembly at surfaces holds the real possibility of becoming a dominating synthesis protocol in 21st century nanotechnologies

Uniquely, the scope and versatility of these molecular architectures at 2D surfaces have been directly captured at the nanoscale via imaging with scanning probe microscopies and advanced surface spectroscopies. At present, however, the field is largely restricted to a 'make and see' approach and there is scarce understanding of any of the parameters that ultimately control molecular surface assembly. For example: (1) molecular assemblies at surfaces show highly polymorphic behaviour, and a priori control of assembly is practically non-existent; (2) little is understood of the influence and balance of the many interactions that drive molecular recognition and assembly (molecule-molecule interactions including dispersion, directional H-bonding and strong electrostatic and covalent interactions); (3) the role of surface-molecule interactions is largely uncharted even though they play a significant role in the diffusion of molecules and their subsequent assembly; (4), there is ample evidence that the kinetics of self-assembly is the major factor in determining the final structure, often driving polymorphic behaviour and leading to widely varied outcomes, depending on the conditions of formation; (5) a gamut of additional surface phenomena also also influence assembly e.g. chemical reactions between molecules, thermally activated internal degrees of freedom of molecules, surface reconstructions and co-assembly via coordinating surface atoms.

The main objective of this project is to advance from experimental phenomena-reporting to knowledge-based design, and its central goal is to identify the role played by thermodynamic, entropic, kinetic and chemical factors in dictating molecular organisation at surfaces under given experimental conditions. To address this challenge requires a two-pronged approach in which ambitious and comprehensive theory development is undertaken alongside powerful imaging and spectroscopic tools applied to the same systems. This synergy of experiment and theory is absolutely essential to develop a fundamental understanding, which would enable a roadmap for controlled and engineered self-assembly at surfaces to be proposed that would, ultimately, allow one to 'dial up' a required structure at will. Four important and qualitatively different classes of assembly at surfaces will be studied: Molecular Self-Assembly; Hierarchical Self-Assembly; Metal-Organic Self Assembly; and, on-surface Covalent Assembly.

Potential Impact:
Dissemination: Research outputs will be published in high impact journals and presented at international conferences, increasing the profile of UK science.

Industry impact:
Results of significance to technology and society will be disseminated to industry, government and public bodies via the dedicated UoL publication 'Research Intelligence'. Key breakthroughs will be publicised through the press offices of KCL and UoL, which have direct links to the media and to all learned societies (e.g. the Royal Society, the RSc, IoP, and the IoM). Work of the project will also be presented at 'Industry Days' being planned by RR, where invited industrial delegates and members of Knowledge Transfer Networks (KTN) in Nanotechnology, Materials, Chemistry and Health will engage with academic researchers and discuss collaboration and partnership. Theoretical advances, relevant to industry, will be disseminated with the help of KCL Business, a gateway for society and businesses to access research outputs at KCL, and the Thomas Young Centre (TYC), where LK is on the Executive Committee. TYC enjoys close contacts with National Physics Laboratory and also with Samsung, UK Defence Industry and BP.

Knowledge Transfer (KT) capability:
The research outputs will be scrutinised by the PIs for possible exploitation, patent protection and commercialisation, aided by the Business divisions from each institution. Both Universities are members of the Russell Group, are strongly committed to staying at the forefront of innovation and research, have a long-established track records of impact resulting from research, and strong cultures for Knowledge Exchange (KE) activities. UoL topped the Russell Group in 2007 for income per academic from KE, is the best performer in KT Partnerships in the northwest of England, and holds an EPSRC KT Account (KTA) to increase the impact and Technology Readiness Level of EPSRC funded research. RR is the KE coordinator for the School of Physical Sciences, has strong experience in engaging with the private sector in her previous role as the Associate Director of the Leverhulme Centre for Innovative Catalysis at UoL and is a member of European research networks with active industrial partnership and has secured international patents. She has also been actively engaged with UoL Business Gateway team regarding IP protection, shareholding agreements and spin-outs.

Public Engagement and Outreach:
RR is PI on a major EPSRC public partnership grant 'Giants of the Infinitesimal' that has created an exhibition on nanoscience for school children (launched in October 2011 at the Manchester Museum of Science and Industry). Additional funds are requested to expand the exhibition to describe self-assembly at surfaces and how such systems could underpin new nanotechnologies, and allow the exhibition to travel to new sites. The Societal Impact of this exhibition will be to make the public aware of the potential of nanoscience, the future applications of research and the responsibilities involved. The topic of self-assembly will form a dedicated zone and will include applications such as organic solar cells, smart displays, electronic paper, etc. At KCL, results of wider significance to technology and society will be disseminated by a dedicated science media liaison person, who will communicate our outcomes to wider mainstream media. There will also be dissemination at weekly Maxwell lectures, hosted by KCL, which are open to the general public. The Physics Department has an active outreach committee, which will ensure that our results become available to several London based secondary schools via seminars and invited lectures. LK has been invited by Highgate School to give presentations about his research. Specifically, London schools from deprived areas will be targeted to increase interest in science, and we request funding to cover the cost for them to visit the Departmen