Quantum chemical study of the effect of precursor stereochemistry on dissociative chemisorption and surface redox reactions during the atomic layer deposition of the transition metal copper

Using quantum chemical calculations, we investigate surface reactions of copper precursors and diethylzinc as the reducing agent for effective Atomic Layer Deposition (ALD) of Cu. The adsorption of various commonly used Cu(II) precursors is explored. The precursors vary in the electronegativity and conjugation of the ligands and flexibility of the whole molecule. Our study shows that the overall stereochemistry of the precursor governs the adsorption onto its surface. Formation of different Cu(II)/Cu(I)/Cu(0) intermediate complexes from the respective Cu(II) compounds on the surface is also explored. The surface model is a (111) facet of a Cu55 cluster. Cu(I) compounds are found to cover the surface after the precursor pulse, irrespective of the precursor chosen. We provide new information about the surface chemistry of Cu(II) versus Cu(I) compounds. A pair of CuEt intermediates or the dimer Cu2Et2 reacts in order to deposit a new Cu atom and release gaseous butane. In this reaction, two electrons from the Et anions are donated to copper for reduction to metallic form. This indicates that a ligand exchange between the Cu and Zn is important for the success of this transmetalation reaction. The effect of the ligands in the precursor on the electron density before and after adsorption onto the surface has also been computed through population analysis. In the Cu(I) intermediate, charge is delocalized between the Cu precursor and the bare copper surface, indicating metallic bonding as the precursor densifies to the surface.

Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Computational study of the growth of copper thin films by atomic layer deposition

Copper is the main interconnect material in microelectronic devices, and a 2 nm-thick continuous Cu film seed layer needs to be deposited to produce microelectronic devices with the smallest features and more functionality. Atomic layer deposition (ALD) is the most suitable method to deposit such thin films. However, the reaction mechanism and the surface chemistry of copper ALD remain unclear, which is deterring the development of better precursors and design of new ALD processes. In this thesis, we study the surface chemistries during ALD of copper by means of density functional theory (DFT). To understand the effect of temperature and pressure on the composition of copper with substrates, we used ab initio atomistic thermodynamics to obtain phase diagram of the Cu(111)/SiO2(0001) interface. We found that the interfacial oxide Cu2O phases prefer high oxygen pressure and low temperature while the silicide phases are stable at low oxygen pressure and high temperature for Cu/SiO2 interface, which is in good agreement with experimental observations. Understanding the precursor adsorption on surfaces is important for understanding the surface chemistry and reaction mechanism of the Cu ALD process. Focusing on two common Cu ALD precursors, Cu(dmap)2 and Cu(acac)2, we studied the precursor adsorption on Cu surfaces by means of van der Waals (vdW) inclusive DFT methods. We found that the adsorption energies and adsorption geometries are dependent on the adsorption sites and on the method used to include vdW in the DFT calculation. Both precursor molecules are partially decomposed and the Cu cations are partially reduced in their chemisorbed structure. It is found that clean cleavage of the ligand−metal bond is one of the requirements for selecting precursors for ALD of metals. 2 Bonding between surface and an atom in the ligand which is not coordinated with the Cu may result in impurities in the thin film. To have insight into the reaction mechanism of a full ALD cycle of Cu ALD, we proposed reaction pathways based on activation energies and reaction energies for a range of surface reactions between Cu(dmap)2 and Et2Zn. The butane formation and desorption steps are found to be extremely exothermic, explaining the ALD reaction scheme of original experimental work. Endothermic ligand diffusion and re-ordering steps may result in residual dmap ligands blocking surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. This may lead to very slow growth rate, as was the case in the experimental work. By investigating the reduction of CuO to metallic Cu, we elucidated the role of the reducing agent in indirect ALD of Cu. We found that CuO bulk is protected from reduction during vacuum annealing by the CuO surface and that H2 is required in order to reduce that surface, which shows that the strength of reducing agent is important to obtain fully reduced metal thin films during indirect ALD processes. Overall, in this thesis, we studied the surface chemistries and reaction mechanisms of Cu ALD processes and the nucleation of Cu to form a thin film.

Three Hundred Years in Annapolis: Phase III Archaeological Investigations of the Anne Arundel County Courthouse Site (18AP63), Annapolis, Maryland

During the summer of 1994, Archaeology in Annapolis conducted archaeological investigations of the city block bounded by Franklin, South and Cathedral Streets in the city of Annapolis. This Phase III excavation was conducted as a means to identify subsurface cultural resources in the impact area associated with the proposed construction of the Anne Arundel County Courthouse addition. This impact area included both the upper and lower parking lots used by Courthouse employees. Investigations were conducted in the form of mechanical trenching and hand excavated units. Excavations in the upper lot area yielded significant information concerning the interior area of the block. Known as Bellis Court, this series of rowhouses was constructed in the late nineteenth century and was used as rental properties by African-Americans. The dwellings remained until the middle of the twentieth century when they were demolished in preparation for the construction of a Courthouse addition. Portions of the foundation of a house owned by William H. Bellis in the 1870s were also exposed in this area. Construction of this house was begun by William Nicholson around 1730 and completed by Daniel Dulany in 1732/33. It was demolished in 1896 by James Munroe, a Trustee for Bellis. Excavations in the upper lot also revealed the remains of a late seventeenth/early eighteenth century wood-lined cellar, believed to be part of the earliest known structure on Lot 58. After an initially rapid deposition of fill around 1828, this cellar was gradually covered with soil throughout the remainder of the nineteenth century. The fill deposit in the cellar feature yielded a mixed assemblage of artifacts that included sherds of early materials such as North Devon gravel-tempered earthenware, North Devon sgraffito and Northem Italian slipware, along with creamware, pearlware and whiteware. In the lower parking lot, numerous artifacts were recovered from yard scatter associated with the houses that at one time fronted along Cathedral Street and were occupied by African- Americans. An assemblage of late seventeenth century/early eighteenth century materials and several slag deposits from an early forge were recovered from this second area of study. The materials associated with the forge, including portions of a crucible, provided evidence of some of the earliest industry in Annapolis. Investigations in both the upper and lower parking lots added to the knowledge of the changing landscape within the project area, including a prevalence of open space in early periods, a surprising survival of impermanent structures, and a gradual regrading and filling of the block with houses and interior courts. Excavations at the Anne Arundel County Courthouse proved this to be a multi-component site, rich in cultural resources from Annapolis' Early Settlement Period through its Modern Period (as specified by Maryland's Comprehensive Historic Preservation Plan (Weissman 1986)). This report provides detailed interpretations of the archaeological findings of these Phase III investigations.

Mechanosensitive neurons on the internal reproductive tract contribute to egg-laying-induced acetic acid attraction in Drosophila.

Selecting a suitable site to deposit their eggs is an important reproductive need of Drosophila females. Although their choosiness toward egg-laying sites is well documented, the specific neural mechanism that activates females' search for attractive egg-laying sites is not known. Here, we show that distention and contraction of females' internal reproductive tract triggered by egg delivery through the tract plays a critical role in activating such search. We found that females start to exhibit acetic acid (AA) attraction prior to depositing each egg but no attraction when they are not laying eggs. Artificially distending the reproductive tract triggers AA attraction in non-egg-laying females, whereas silencing the mechanosensitive neurons we identified that can sense the contractile status of the tract eliminates such attraction. Our work uncovers the circuit basis of an important reproductive need of Drosophila females and provides a simple model for dissecting the neural mechanism that underlies a reproductive need-induced behavioral modification.

Mix it and fix it: functions of composite olfactory signals in ring-tailed lemurs.

Animals communicating via scent often deposit composite signals that incorporate odorants from multiple sources; however, the function of mixing chemical signals remains understudied. We tested both a 'multiple-messages' and a 'fixative' hypothesis of composite olfactory signalling, which, respectively, posit that mixing scents functions to increase information content or prolong signal longevity. Our subjects-adult, male ring-tailed lemurs (Lemur catta)-have a complex scent-marking repertoire, involving volatile antebrachial (A) secretions, deposited pure or after being mixed with a squalene-rich paste exuded from brachial (B) glands. Using behavioural bioassays, we examined recipient responses to odorants collected from conspecific strangers. We concurrently presented pure A, pure B and mixed A + B secretions, in fresh or decayed conditions. Lemurs preferentially responded to mixed over pure secretions, their interest increasing and shifting over time, from sniffing and countermarking fresh mixtures, to licking and countermarking decayed mixtures. Substituting synthetic squalene (S)-a well-known fixative-for B secretions did not replicate prior results: B secretions, which contain additional chemicals that probably encode salient information, were preferred over pure S. Whereas support for the 'multiple-messages' hypothesis underscores the unique contribution from each of an animal's various secretions, support for the 'fixative' hypothesis highlights the synergistic benefits of composite signals.

Destination municipal solid waste in the city of Buenos Aires : brief diagnosis and some alternatives

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The numerical modelling of multi-physics phenomena: The shape casting process

In this paper a computer simulation tool capable of modelling multi-physics processes in complex geometry has been developed and applied to the casting process. The quest for high-quality complex casting components demanded by the aerospace and automobile industries, requires more precise numerical modelling techniques and one that need to be generic and modular in its approach to modelling multi-processes problems. For such a computer model to be successful in shape casting, the complete casting process needs to be addressed, the major events being:-• Filling of hot liquid metal into a cavity mould • Solidification and latent heat evolution of liquid metal • Convection currents generated in liquid metal by thermal gradients • Deformation of cast and stress development in solidified metal • Macroscopic porosity formation The above phenomena combines the analysis of fluid flow, heat transfer, change of phase and thermal stress development. None of these events can be treated in isolation as they inexorably interact with each other in a complex way. Also conditions such as design of running system, location of feeders and chills, moulding materials and types of boundary conditions can all affect on the final cast quality and must be appropriately represented in the model.

Case-based retrieval of 3-dimensional shapes for the design of metal castings

This paper describes research into retrieval based on 3-dimensional shapes for use in the metal casting industry. The purpose of the system is to advise a casting engineer on the design aspects of a new casting by reference to similar castings which have been prototyped and tested in the past. The key aspects of the system are the orientation of the shape within the mould, the positions of feeders and chills, and particular advice concerning special problems and solutions, and possible redesign. The main focus of this research is the effectiveness of similarity measures based on 3-dimensional shapes. The approach adopted here is to construct similarity measures based on a graphical representation deriving from a shape decomposition used extensively by experienced casting design engineers. The paper explains the graphical representation and discusses similarity measures based on it. Performance measures for the CBR system are given, and the results for trials of the system are presented. The competence of the current case-base is discussed, with reference to a representation of cases as points in an n-dimensional feature space, and its principal components visualization. A refinement of the case base is performed as a result of the competence analysis and the performance of the case-base before and after refinement is compared.

Return of deposits

Explores case law illustrating the circumstances in which the courts are likely to order the return of a deposit in the event of a buyer's default. Notes the unwillingness of the courts to apply the rule on penalties to deposits and discusses the court's discretion under the Law of Property Act 1925 s.49(2) to order repayment. Focuses on the Chancery Division ruling in Aribisala v St James Homes (Grosvenor Dock) Ltd giving guidance on the circumstances in which the discretion under s.49(2) should be exercised.

Returning to deposits...

Examines the Court of Appeal ruling in Midill (97PL) Ltd v Park Lane Estates Ltd on whether the court should exercise its discretion to return a deposit paid under a contract for the sale of a property where, despite the claimant having defaulted on its purchase, the owner obtained a higher price than would have been paid by the claimant when it subsequently sold the property to a third party. Considers the need for special or exceptional circumstances to be present to override the rule that deposits were to be forfeited upon the purchaser's default.

The use of biological indicators of heavy metal contamination in estuaries. Occasional Publication of the Marine Biological Association 1

The use of the deposit-feeding molluscs Scrobicularia plana and Macoma balthica and the burrowing polychaete Nereis diversicolor as indicators of the biological availability of heavy metals in sediments has been evaluated. Concentrations of Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sn and Zn have been measured in organisms and sediments from more than 30 estuaries in south west England and South Wales and indicate that the biological availability of most metals varies by order of magnitude between uncontaminated and contaminated sites. The results have been compared with those obtained with the use of other species of indicator organisms in estuaries.

Ranking of length-class seasonal and regional effects on dietary compositions of the co-occurring Pagrus auratus (Sparidae) and Pseudocaranx georgianus (Carangidae)

Using an effective combination of multivariate testing and ordination analyses, this study compares the extents to which the diets of two co-occurring fish species (Pagrus auratus and Pseudocaranx georgianus) are related to body size (length class), season and region and the rank order importance of those effects. Thus, volumetric dietary compositions were determined for these species on the lower west coast of Australia, where both are abundant, and for P. auratus from the mid west coast and P. georgianus from the south coast. The diet of P. auratus on the lower west coast was strongly related to body size and slightly less to season. With increasing body size, its diet shifted from predominantly ophiuroids to larger prey, such as brachyuran crabs, teleosts, echinoids and ultimately asteroids, probably reflecting a shift from foraging over soft sediments to areas over and around reefs. Seasonal changes on the lower west coast were restricted mainly to small P. auratus, while larger fish underwent seasonal changes further north. Analyses using a common size range of medium to larger P. auratus demonstrated that dietary composition differed more between regions than seasons. The relationships between diet and length class of P. georgianus on both the lower west and south coasts were less pronounced than for P. auratus and seasonal changes were restricted to the south coast, where amphipod consumption increased markedly in summer. The diet of P. georgianus was related far more to region than length class and season, with more small teleosts, small crabs, carideans and littorinids and less amphipods, isopods and small bivalves being ingested on the lower west than south coasts. Although crabs and teleosts were important typifying prey of P. auratus and P. georgianus, when co-occurring, the former predator tended to ingest greater volumes of larger and often less mobile prey. This reflects differences in dentition, jaw morphology and feeding behaviour and reduces the potential for competition for food resources. The results imply that P. auratus and P. georgianus are opportunistic feeders and that the effects of length class, season and region on dietary composition and their rank orders can vary markedly between species and for length class and season between regions for the same species.

Can the Continuous Plankton Recorder (CPR) be used to infer sardine diet?

Knowledge on the impact of climate variability in the diet of planktivorous fish is limited by the laborious work involved in stomach content analysis, impractical for large scale studies. Routine measurements of plankton such as the Continuous Plankton Recorder (CPR) survey provide valuable information of the temporal variation of phyto- and zooplankton prey availability for higher trophic levels. Sardines are a world-wide distributed and commercially important planktivorous fish, at the basis of the pelagic marine food web. Being predominantly non-selective filter-feeders, their diets closely correspond to the water plankton species and a significant relationship was recently found between Sardina pilchardus feeding intensity and remotely sensed chlorophyll alpha . Data of sardine stomach prey composition and CPR were obtained during 2003 for the same location off the west coast of Portugal, an area characterised by strong seasonality of plankton abundance and composition, mainly governed by upwelling events. Phyto- and zooplankton prey in sardine stomachs were identified to the lowest possible taxa and their numerical and volumetric abundance was registered, as well as their contribution to the prey carbon content. The seasonal variation of the abundance and composition of sardine diet was then compared to the abundance and composition of the water plankton obtained with the CPR at the same time and for the same area where the fish were collected, in order to evaluate if CPR data can be used to proxy sardine prey availability and diet composition at large temporal scales.