Photocatalytic activities of tin(IV) oxide surface-modified titanium(IV) dioxide show a strong sensitivity to the TiO 2 crystal form

Surface modification of rutile TiO2 with extremely small SnO2 clusters gives rise to a great increase in its UV light activity for degradation of model organic water pollutants, while the effect is much smaller for anatase TiO2. This crystal form sensitivity is rationalized in terms of the difference in the electronic modification of TiO2 through the interfacial Sn−O−Ti bonds. The increase in the density of states near the conduction band minimum of rutile by hybridization with the SnO2 cluster levels intensifies the light absorption, but this is not seen with modified anatase. The electronic transition from the valence band to the conduction band causes the bulk-to-surface interfacial electron transfer to enhance charge separation. Further, electrons relaxed to the conduction minimum are smoothly transferred to O2 due to the action of the SnO2 species as an electron transfer promoter.

Experimental analysis of novel telecom source materials and devices

Incumbent telecommunication lasers emitting at 1.5 µm are fabricated on InP substrates and consist of multiple strained quantum well layers of the ternary alloy InGaAs, with barriers of InGaAsP or InGaAlAs. These lasers have been seen to exhibit very strong temperature dependence of the threshold current. This strong temperature dependence leads to a situation where external cooling equipment is required to stabilise the optical output power of these lasers. This results in a significant increase in the energy bill associated with telecommunications, as well as a large increase in equipment budgets. If the exponential growth trend of end user bandwidth demand associated with the internet continues, these inefficient lasers could see the telecommunications industry become the dominant consumer of world energy. For this reason there is strong interest in developing new, much more efficient telecommunication lasers. One avenue being investigated is the development of quantum dot lasers on InP. The confinement experienced in these low dimensional structures leads to a strong perturbation of the density of states at the band edge, and has been predicted to result in reduced temperature dependence of the threshold current in these devices. The growth of these structures is difficult due to the large lattice mismatch between InP and InAs; however, recently quantum dots elongated in one dimension, known as quantum dashes, have been demonstrated. Chapter 4 of this thesis provides an experimental analysis of one of these quantum dash lasers emitting at 1.5 µm along with a numerical investigation of threshold dynamics present in this device. Another avenue being explored to increase the efficiency of telecommunications lasers is bandstructure engineering of GaAs-based materials to emit at 1.5 µm. The cause of the strong temperature sensitivity in InP-based quantum well structures has been shown to be CHSH Auger recombination. Calculations have shown and experiments have verified that the addition of bismuth to GaAs strongly reduces the bandgap and increases the spin orbit splitting energy of the alloy GaAs1−xBix. This leads to a bandstructure condition at x = 10 % where not only is 1.5 µm emission achieved on GaAs-based material, but also the bandstructure of the material can naturally suppress the costly CHSH Auger recombination which plagues InP-based quantum-well-based material. It has been predicted that telecommunications lasers based on this material system should operate in the absence of external cooling equipment and offer electrical and optical benefits over the incumbent lasers. Chapters 5, 6, and 7 provide a first analysis of several aspects of this material system relevant to the development of high bismuth content telecommunication lasers.

Forces of agglomeration and dispersal in rural business networks: a social network analysis

Two concepts in rural economic development policy have been the focus of much research and policy action: the identification and support of clusters or networks of firms and the availability and adoption by rural businesses of Information and Communication Technologies (ICT). From a theoretical viewpoint these policies are based on two contrasting models, with clustering seen as a process of economic agglomeration, and ICT-mediated communication as a means of facilitating economic dispersion. The study’s conceptual framework is based on four interrelated elements: location, interaction, knowledge, and advantage, together with the concept of networks which is employed as an operationally and theoretically unifying concept. The research questions are developed in four successive categories: Policy, Theory, Networks, and Method. The questions are approached using a study of two contrasting groups of rural small businesses in West Cork, Ireland: (a) Speciality Foods, and (b) firms in Digital Products and Services. The study combines Social Network Analysis (SNA) with Qualitative Thematic Analysis, using data collected from semi-structured interviews with 58 owners or managers of these businesses. Data comprise relational network data on the firms’ connections to suppliers, customers, allies and competitors, together with linked qualitative data on how the firms established connections, and how tacit and codified knowledge was sourced and utilised. The research finds that the key characteristics identified in the cluster literature are evident in the sample of Speciality Food businesses, in relation to flows of tacit knowledge, social embedding, and the development of forms of social capital. In particular the research identified the presence of two distinct forms of collective social capital in this network, termed “community” and “reputation”. By contrast the sample of Digital Products and Services businesses does not have the form of a cluster, but matches more closely to dispersive models, or “chain” structures. Much of the economic and social structure of this set of firms is best explained in terms of “project organisation”, and by the operation of an individual rather than collective form of “reputation”. The rural setting in which these firms are located has resulted in their being service-centric, and consequently they rely on ICT-mediated communication in order to exchange tacit knowledge “at a distance”. It is this factor, rather than inputs of codified knowledge, that most strongly influences their operation and their need for availability and adoption of high quality communication technologies. Thus the findings have applicability in relation to theory in Economic Geography and to policy and practice in Rural Development. In addition the research contributes to methodological questions in SNA, and to methodological questions about the combination or mixing of quantitative and qualitative methods.