Electron transport in molecular systems

The remarkable advances in nanoscience and nanotechnology over the last two decades allow one to manipulate individuals atoms, molecules and nanostructures, make it possible to build devices with only a few nanometers, and enhance the nano-bio fusion in tackling biological and medical problems. It complies with the ever-increasing need for device miniaturization, from magnetic storage devices, electronic building blocks for computers, to chemical and biological sensors. Despite the continuing efforts based on conventional methods, they are likely to reach the fundamental limit of miniaturization in the next decade, when feature lengths shrink below 100 nm. On the one hand, quantum mechanical efforts of the underlying material structure dominate device characteristics. On the other hand, one faces the technical difficulty in fabricating uniform devices. This has posed a great challenge for both the scientific and the technical communities. The proposal of using a single or a few organic molecules in electronic devices has not only opened an alternative way of miniaturization in electronics, but also brought up brand-new concepts and physical working mechanisms in electronic devices. This thesis work stands as one of the efforts in understanding and building of electronic functional units at the molecular and atomic levels. We have explored the possibility of having molecules working in a wide spectrum of electronic devices, ranging from molecular wires, spin valves/switches, diodes, transistors, and sensors. More specifically, we have observed significant magnetoresistive effect in a spin-valve structure where the non-magnetic spacer sandwiched between two magnetic conducting materials is replaced by a self-assembled monolayer of organic molecules or a single molecule (like a carbon fullerene). The diode behavior in donor(D)-bridge(B)-acceptor(A) type of single molecules is then discussed and a unimolecular transistor is designed. Lastly, we have proposed and primarily tested the idea of using functionalized electrodes for rapid nanopore DNA sequencing. In these studies, the fundamental roles of molecules and molecule-electrode interfaces on quantum electron transport have been investigated based on first-principles calculations of the electronic structure. Both the intrinsic properties of molecules themselves and the detailed interfacial features are found to play critical roles in electron transport at the molecular scale. The flexibility and tailorability of the properties of molecules have opened great opportunity in a purpose-driven design of electronic devices from the bottom up. The results that we gained from this work have helped in understanding the underlying physics, developing the fundamental mechanism and providing guidance for future experimental efforts.

Evaluating stress patterns for Plio-Quaternary brittle deformation along the Calama-Olacapato-El Toro fault zone, Central Andes

Understanding the geometry and kinematics of the major structures of an orogen is important to elucidate its style of deformation, as well as its tectonic evolution. We describe the temporal and spatial changes in the state of stress of the trans-orogen area of the Calama-Olacapato-El Toro (COT) Fault Zone in the Central Andes, at about 24°S within the northern portion of the Puna Plateau between the Argentina-Chile border. The importance of the COT derives principally from the Quaternary-Holocene activity recognized on some segments, which may shed new light on its possible control on Quaternary volcanism and on the seismic hazard evaluation of the area. Field geological surveys along with kinematic analysis and numerical inversion of ∼140 new fault-slip measurements have revealed that this portion of the COT zone, previously considered a continuous, long-lived lineament, in reality has been subjected to three different kinematic regimes: 1) a Miocene transpressional phase with the maximum principal stress (σ1) chiefly trending NNE-SSW; 2) an extensional phase that started by 9 Ma, with a horizontal NW-SE-striking minimum principal stress (σ3) – permutations between σ2 and σ3 axes have been recognized at two sites – and 3) a left-lateral strike-slip phase with a horizontal ∼E-W &sigma1 and ∼N-S σ3 dating to the Late Pliocene-Quaternary. Spatially, in the Quaternary, the left-lateral component decreases toward the westernmost tip of the COT, where it transitions to extension; this produced to a N-S horst and graben structure. Hence, even if transcurrence is still active in the eastern portion of the COT, as focal mechanisms of crustal earthquakes indicate, our study demonstrates that extension is becoming the predominant structural style of deformation, at least in the western region. These major temporal and spatial changes in the tectonic regimes are attributed in part to changes in the magnitude of the boundary forces due to subduction processes. The overall orogen-perpendicular extension might be the result of vertical stress larger than both the horizontal stresses induced by gravitational effect of a thickened crust.