Atomistic simulations of nanoscale molecular and metal oxide junctions

The push to continually improve computing power through the further miniaturisation of electronic devices has led to an explosion of "post-Moore" technologies such as molecular electronics and quantum computing. The downscaling of electronic devices has enhanced the importance of quantum effects. As a result to aid in the understanding and development of new devices, accurate and efficient atomistic material modelling methods are crucial for guiding experiments. In this thesis first principle material modelling (e.g Density Functional Theory) is combined with the atomistic Non Equilibrium Green’s Function quantum transport method to study how the electronic structure of two interesting junction systems relate to the electron transport through the junction. These two types of junctions, molecular and metal oxide, have crucial roles to play in the development of molecular based memories and superconducting quantum computing respectively. The first half of this thesis shows how the electronic structure of Polyoxometalate molecules dominate their electron transport properties whilst their redox ability makes them promising for memory applications. The results of the simulations reveal how the charge-balancing counterions of Polyoxometalates increase the conductance of the molecular junctions by stabilisation of unoccupied states, this is a key discovery as the effect of counterions are typically ignored. Polyoxometalates can be altered easily by changing the identity of the central caged atom, enhancing device engineering possibilities. The IV characteristics and capacitance are computed for Polyoxometalates with different caged atoms, the results show how the charge transport and storage can be engineered by choice of caged species and redox state. In the second half of this work, the archetypal Josephson junction, Al/AlOx/Al is explored. The goal was to understand from an atomistic point of view how the nature of the amorphous barrier influences the electron transport. The calculations provide evidence that the oxide concentration of the amorphous barrier significantly influences the resistance of the junction, it is found that oxygen deficient barriers lead to higher than expected critical currents. Unexpectedly the simulations here fail to show an exponential relationship between barrier length and resistance of the device. It is argued that there is an effective barrier length smaller than the physical barrier length due to thinner regions of the barrier. This highlights how important an understanding of the atomic structure of these junctions are for designing high quality junctions for superconducting qubits

Influence of the contact geometry and counterions on the current flow and charge transfer in polyoxometalate molecular junctions: a density functional theory study

Polyoxometalates (POMs) are promising candidates for molecular electronic applications because (1) they are inorganic molecules, which have better CMOS compatibility compared to organic molecules; (2) they are easily synthesized in a one-pot reaction from metal oxides (MOx) (where the metal M can be, e.g., W, V, or Mo, and x is an integer between 4 and 7); (3) POMs can self-assemble to form various shapes and configurations, and thus the chemical synthesis can be tailored for specific device performance; and (4) they are redox-active with multiple states that have a very low voltage switching between polarized states. However, a deep understanding is required if we are to make commercial molecular devices a reality. Simulation and modeling are the most time efficient and cost-effective methods to evaluate a potential device performance. Here, we use density functional theory in combination with nonequilibrium Green’s function to study the transport properties of [W18O54(SO3)2]4–, a POM cluster, in a variety of molecular junction configurations. Our calculations reveal that the transport profile not only is linked to the electronic structure of the molecule but also is influenced by contact geometry and presence of ions. More specifically, the contact geometry and the number of bonds between the POM and the electrodes determine the current flow. Hence, strong and reproducible contact between the leads and the molecule is mandatory to establish a reliable fabrication process. Moreover, although often ignored, our simulations show that the charge balancing counterions activate the conductance channels intrinsic to the molecule, leading to a dramatic increase in the computed current at low bias. Therefore, the role of these counterions cannot be ignored when molecular based devices are fabricated. In summary, this work shows that the current transport in POM junctions is determined by not only the contact geometry between the molecule and the electrode but also the presence of ions around the molecule. This significantly impacts the transport properties in such nanoscale molecular electronic devices

New discoveries at Woolsey Mound, MC118, northern Gulf of Mexico

Woolsey Mound, a 1km-diameter carbonate-gas hydrate complex in the northern Gulf of Mexico, is the site of the Gulf’s only seafloor monitoring station-observatory in its only research reserve, Mississippi Canyon 118. Active venting, outcropping hydrate, and a thriving chemosynthetic community recommend the site for study. Since 2005, the Gulf of Mexico Hydrates Research Consortium has been conducting multidisciplinary studies to 1. Characterize the site, 2. Establish a facility for real-time monitoring-observing of gas hydrates in a natural setting, 3. Study the effects of gas hydrates on seafloor stability, 4. Establish fluid migration routes and estimates of fluid-flux at the site, 5. Establish the interrelationships between the organisms at the vent site and the association-dissociation of hydrates. A variety of novel geological, geophysical, geochemical and biological studies has been designed and conducted, some in survey mode, others in monitoring mode. Geophysical studies involving merging multiple seismic data acquisition systems accompanied by the application of custom processing techniques verify communication of surface features with deep structures. Supporting geological data derive from innovative recovery techniques. Geochemical sensors, used experimentally in survey mode, including aboard an AUV, double as monitoring devices. A suite of pore-fluid sampling devices has returned data that capture change at the site in daily increments; using only noise as an energy source, hydrophones have returned daily fluctuations in physical properties. Ever-expanding capabilities of a custom-ROV have been determined by research needs. Processing of new as well as conventional data via unconventional means has resulted in the discovery of new features…..vents, faults, benthic fauna…..and modification of others including pockmarks, hydrate outcrops, vent activity, and water-column chemical plumes. Though real-time monitoring awaits communications and power link to land, periodic data-collection reveals a carbonate-hydrate mound, part of an immensely complex hydrocarbon system

Attitudes and Practices Among Internists Concerning Genetic Testing

Many questions remain concerning whether, when, and how physicians order genetic tests, and what factors are involved in their decisions. We surveyed 220 internists from two academic medical centers about their utilization of genetic testing. Rates of genetic utilizations varied widely by disease. Respondents were most likely to have ordered tests for Factor V Leiden (16.8 %), followed by Breast/Ovarian Cancer (15.0 %). In the past 6 months, 65 % had counseled patients on genetic issues, 44 % had ordered genetic tests, 38.5 % had referred patients to a genetic counselor or geneticist, and 27.5 % had received ads from commercial labs for genetic testing. Only 4.5 % had tried to hide or disguise genetic information, and <2 % have had patients report genetic discrimination. Only 53.4 % knew of a geneticist/genetic counselor to whom to refer patients. Most rated their knowledge as very/somewhat poor concerning genetics (73.7 %) and guidelines for genetic testing (87.1 %). Most felt needs for more training on when to order tests (79 %), and how to counsel patients (82 %), interpret results (77.3 %), and maintain privacy (80.6 %). Physicians were more likely to have ordered a genetic test if patients inquired about genetic testing (p  < .001), and if physicians had a geneticist/genetic counselor to whom to refer patients (p  < .002), had referred patients to a geneticist/genetic counselor in the past 6 months, had more comfort counseling patients about testing (p  < .019), counseled patients about genetics, larger practices (p  < .032), fewer African‐American patients (p  < .027), and patients who had reported genetic discrimination (p  < .044). In a multiple logistic regression, ordering a genetic test was associated with patients inquiring about testing, having referred patients to a geneticist/genetic counselor and knowing how to order tests. These data suggest that physicians recognize their knowledge deficits, and are interested in training. These findings have important implications for future medical practice, research, and education

Use of SMS texts for facilitating access to online alcohol interventions: a feasibility study

A41 Use of SMS texts for facilitating access to online alcohol interventions: a feasibility study In: Addiction Science & Clinical Practice 2017, 12(Suppl 1): A4

Proceedings of the 13th annual conference of INEBRIA

CITATION: Watson, R., et al. 2016. Proceedings of the 13th annual conference of INEBRIA. Addiction Science & Clinical Practice, 11:13, doi:10.1186/s13722-016-0062-9.The original publication is available at https://ascpjournal.biomedcentral.comENGLISH SUMMARY : Meeting abstracts.https://ascpjournal.biomedcentral.com/articles/10.1186/s13722-016-0062-9Publisher's versio

Computational study of oxide stoichiometry and variability in the Al/AlOx/Al tunnel junction

Aluminium tunnel junctions are key components of a wide variety of electronic devices. These superconducting tunnel junctions, known as Josephson Junctions (JJ's) are one of the main components of superconducting qubits, a favourite qubit technology in the race for working quantum computers. In this simulation study our JJ configurations are modelled as two aluminium electrodes which are separated by a thin layer of amorphous aluminium oxide. There is limited understanding of how the structure of the amorphous oxide barrier affects the performance and shortcomings of JJ systems. In this paper we present a computational study which combines molecular dynamics, atomistic semi-empirical methods (Density Functional Tight Binding) and non-equilibrium Green's function to study the electronic structure and current flow of these junction devices. Our results suggest that the atomic nature of the amorphous barrier linked to aluminum-oxygen coordination sensitively affects the current–voltage (IV) characteristics, resistance and critical current. Oxide stoichiometry is an important parameter that can lead to variation in resistance and critical currents of several orders of magnitude. The simulations further illustrate the variability that arises due to small differences in atomic structure across amorphous barriers with the same stoichiometry, density and barrier length. Our results also confirm that the charge transport through the barrier is dominated by metallic conduction pathways