Growth, modification and integration of carbon nanotubes into molecular electronics

Molecules are the smallest possible elements for electronic devices, with active elements for such devices typically a few Angstroms in footprint area. Owing to the possibility of producing ultrahigh density devices, tremendous effort has been invested in producing electronic junctions by using various types of molecules. The major issues for molecular electronics include (1) developing an effective scheme to connect molecules with the present micro- and nano-technology, (2) increasing the lifetime and stabilities of the devices, and (3) increasing their performance in comparison to the state-of-the-art devices. In this work, we attempt to use carbon nanotubes (CNTs) as the interconnecting nanoelectrodes between molecules and microelectrodes. The ultimate goal is to use two individual CNTs to sandwich molecules in a cross-bar configuration while having these CNTs connected with microelectrodes such that the junction displays the electronic character of the molecule chosen. We have successfully developed an effective scheme to connect molecules with CNTs, which is scalable to arrays of molecular electronic devices. To realize this far reaching goal, the following technical topics have been investigated. 1. Synthesis of multi-walled carbon nanotubes (MWCNTs) by thermal chemical vapor deposition (T-CVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques (Chapter 3). We have evaluated the potential use of tubular and bamboo-like MWCNTs grown by T-CVD and PE-CVD in terms of their structural properties. 2. Horizontal dispersion of MWCNTs with and without surfactants, and the integration of MWCNTs to microelectrodes using deposition by dielectrophoresis (DEP) (Chapter 4). We have systematically studied the use of surfactant molecules to disperse and horizontally align MWCNTs on substrates. In addition, DEP is shown to produce impurityfree placement of MWCNTs, forming connections between microelectrodes. We demonstrate the deposition density is tunable by both AC field strength and AC field frequency. 3. Etching of MWCNTs for the impurity-free nanoelectrodes (Chapter 5). We show that the residual Ni catalyst on MWCNTs can be removed by acid etching; the tip removal and collapsing of tubes into pyramids enhances the stability of field emission from the tube arrays. The acid-etching process can be used to functionalize the MWCNTs, which was used to make our initial CNT-nanoelectrode glucose sensors. Finally, lessons learned trying to perform spectroscopic analysis of the functionalized MWCNTs were vital for designing our final devices. 4. Molecular junction design and electrochemical synthesis of biphenyl molecules on carbon microelectrodes for all-carbon molecular devices (Chapter 6). Utilizing the experience gained on the work done so far, our final device design is described. We demonstrate the capability of preparing patterned glassy carbon films to serve as the bottom electrode in the new geometry. However, the molecular switching behavior of biphenyl was not observed by scanning tunneling microscopy (STM), mercury drop or fabricated glassy carbon/biphenyl/MWCNT junctions. Either the density of these molecules is not optimum for effective integration of devices using MWCNTs as the nanoelectrodes, or an electroactive contaminant was reduced instead of the ionic biphenyl species. 5. Self-assembly of octadecanethiol (ODT) molecules on gold microelectrodes for functional molecular devices (Chapter 7). We have realized an effective scheme to produce Au/ODT/MWCNT junctions by spanning MWCNTs across ODT-functionalized microelectrodes. A percentage of the resulting junctions retain the expected character of an ODT monolayer. While the process is not yet optimized, our successful junctions show that molecular electronic devices can be fabricated using simple processes such as photolithography, self-assembled monolayers and dielectrophoresis.

Recurrent voluminous sector collapses at Volcán Barú, Panama

Two volcanic debris avalanche deposits (VDADs), both attributed to sector collapse at Volcán Barú, Panama, have been identified after an investigation of deposits that covered more than a thousand square kilometers. The younger Barriles Deposit is constrained by two radiocarbon ages that are ~9 ka; the older Caisán Deposit is at or beyond the radiocarbon range, >43,500 ybp. The total runout length of the Caisán Deposit was ~50 km and it covers 1190 km2. The Barriles Deposit extended to about 45 km and covered an area of 966 km2, overlapping most of the Caisán. The VDADs are blanketed by pyroclastic deposits and contain a predominance of andesitic material likely representing volcanic dome rock which accumulated above the active vent at Barú before collapsing. Despite heavy vegetation in the field area, over 4000 individual hummocks were digitized from aerial photography. Statistical analysis of hummock locations and geometries depict flow patterns of highly- fragmented material reflecting the effects of underlying topography and also help to define the limit of Barriles’ shorter termination. Barriles and Caisán are primarily unconfined, subaerial volcanic deposits that are among the world’s most voluminous. Calculated through two different geospatial processes, thickness values from field measurements and inferences yield volumes >30 km23 for both deposits. VDADs of comparable scale come from Mount Shasta, USA; Socompa, Chile/Argentina; and Shiveluch, Russia. Currently, the modern edifice is 200-400m lower than the pre-collapse Barriles and Caisán summits and only 16-25% of the former edifice has been replaced since the last failure.

GROUND-BASED AND SATELLITE REMOTE SENSING OF PAROXYSMAL ERUPTIONS AT ETNA VOLCANO, 2011-2012.

Mt Etna's activity has increased during the last decade with a tendency towards more explosive eruptions that produce paroxysmal lava fountains. From January 2011 to April 2012, 25 lava fountaining episodes took place at Etna's New South-East Crater (NSEC). Improved understanding of the mechanism driving these explosive basaltic eruptions is needed to reduce volcanic hazards. This type of activity produces high sulfur dioxide (SO2) emissions, associated with lava flows and ash fall-out, but to date the SO2 emissions associated with Etna's lava fountains have been poorly constrained. The Ultraviolet (UV) Ozone Monitoring Instrument (OMI) on NASA's Aura satellite and the Atmospheric Infrared Sounder (AIRS) on Aqua were used to measure the SO2 loadings. Ground-based data from the Observatoire de Physique du Globe de Clermont-Ferrand (OPGC) L-band Doppler radar, VOLDORAD 2B, used in collaboration with the Italian National Institute of Geophysics and Volcanology in Catania (INGV-CT), also detected the associated ash plumes, giving precise timing and duration for the lava fountains. This study resulted in the first detailed analysis of the OMI and AIRS SO2 data for Etna's lava fountains during the 2011-2012 eruptive cycle. The HYSPLIT trajectory model is used to constrain the altitude of the observed SO2 clouds, and results show that the SO2 emission usually coincided with the lava fountain peak intensity as detected by VOLDORAD. The UV OMI and IR AIRS SO2 retrievals permit quantification of the SO2 loss rate in the volcanic SO2 clouds, many of which were tracked for several days after emission. A first attempt to quantitatively validate AIRS SO2 retrievals with OMI data revealed a good correlation for high altitude SO2 clouds. Using estimates of the emitted SO2 at the time each paroxysm, we observe a correlation with the inter-paroxysm repose time. We therefore suggest that our data set supports the collapsing foam (CF) model [1] as driving mechanism for the paroxysmal events at the NSEC. Using VOLDORAD-based estimates of the erupted magma mass, we observe a large excess of SO2 in the eruption clouds. Satellite measurements indicate that SO2 emissions from Etnean lava fountains can reach the lower stratosphere and hence could pose a hazard to aviation. [1] Parfitt E.A (2004). A discussion of the mechanisms of explosive basaltic eruptions. J. Volcanol. Geotherm. Res. 134, 77-107.