Cooperation between adsorbates accounts for the activation of atomic layer deposition reactions

Atomic layer deposition (ALD) is a technique for producing conformal layers of nanometre-scale thickness, used commercially in non-planar electronics and increasingly in other high-tech industries. ALD depends on self-limiting surface chemistry but the mechanistic reasons for this are not understood in detail. Here we demonstrate, by first-principle calculations of growth of HfO2 from Hf(N(CH3)2)4–H2O and HfCl4–H2O and growth of Al2O3 from Al(CH3)3–H2O, that, for all these precursors, co-adsorption plays an important role in ALD. By this we mean that previously-inert adsorbed fragments can become reactive once sufficient numbers of molecules adsorb in their neighbourhood during either precursor pulse. Through the calculated activation energies, this ‘cooperative’ mechanism is shown to have a profound influence on proton transfer and ligand desorption, which are crucial steps in the ALD cycle. Depletion of reactive species and increasing coordination cause these reactions to self-limit during one precursor pulse, but to be re-activated via the cooperative effect in the next pulse. This explains the self-limiting nature of ALD.

The emerging strategic partnership between the European Union and the African Union

Many among the emerging generation of political elites in Africa see the role the European Union (EU) plays in the maintenance of an unprecedented period of peace in Western Europe as an inspirational example of the manner in which the African Union (AU) can contribute to peace and stability in Africa. This doctoral thesis examines security cooperation between the EU and the AU, with a particular focus on the nature and substance of that cooperation. It suggests that despite the establishment of various EU–AU institutions and ties with a role in security policy and cooperation, such security cooperation is limited in substance. This study argues that EU–AU security cooperation is especially constrained by the emergence of alternative partners, most notably China, and by failures of implementation and follow-through. Two case studies, the first dealing with EU–AU cooperation in peacekeeping, and the second addressing the silent water crisis along with the link between water and security, have been analysed in detail to determine the effectiveness and sustainability of the EU–AU partnership. A number of important lessons for regionalism, interregionalism and multilateralism are drawn from the bond between the EU and the AU. This doctoral thesis will prove that, despite an emphasis on the problematic term ‘strategic’ by both EU and AU policymakers, EU–AU cooperation is limited and somewhat lacking in strategic direction. The cooperation between the EU and the AU focuses mainly on EU financial support for AU peacekeeping and specific projects in Africa (e.g. in the water sector), as well as on a limited political dialogue. Nonetheless, the EU–AU link represents the most comprehensive partnership the AU has with any non-African actor. This study will furthermore demonstrate that the United Nations (UN) is an indispensable third-party to their relationship and it is therefore more appropriate to speak of the AU–EU–UN nexus. This doctoral thesis concludes that the AU–EU–UN nexus is an important example of interregionalism in a global context and that such interregionalism is an important emerging part of global governance.

A benchmark comparison between reconfigurable, intelligent and autonomous wireless inertial measurement and photonic technologies in rehabilitation

Advanced sensory systems address a number of major obstacles towards the provision for cost effective and proactive rehabilitation. Many of these systems employ technologies such as high-speed video or motion capture to generate quantitative measurements. However these solutions are accompanied by some major limitations including extensive set-up and calibration, restriction to indoor use, high cost and time consuming data analysis. Additionally many do not quantify improvement in a rigorous manner for example gait analysis for 5 minutes as opposed to 24 hour ambulatory monitoring. This work addresses these limitations using low cost, wearable wireless inertial measurement as a mobile and minimal infrastructure alternative. In cooperation with healthcare professionals the goal is to design and implement a reconfigurable and intelligent movement capture system. A key component of this work is an extensive benchmark comparison with the 'gold standard' VICON motion capture system.