Structural aspects of redox-mediated electron tunneling (Dedicated to the memory of professor Alexander M. Kuznetsov)

We investigated structural aspects of electron transfer (ET) in tunneling junctions (Au(1 1 1)vertical bar FcN vertical bar solution gap vertical bar Au STM tip) with four different redox-active N-thioalk(ano)ylferrocenes (FcN) embedded. The investigated molecules consist of a redox-active ferrocene (Fc) moiety connected via alkyl spacers with N = 4, 6, 8 and 11 carbon atoms to a thiol anchoring group. We found that for short FcNs (N = 4, 6,8) the redox-mediated ET response increases with the increase of the alkyl chain length, while no enhancement of the ET was observed for Fc1 1. The model of two-step ET with partial vibrational relaxation by Kuznetsov and Ulstrup was used to rationalize these results. The theoretical ET steps were assigned to two processes: (1) electron tunneling from the Fc group to the Au tip through the electrolyte layer and (2) electron transport from the Au(1 1 1) substrate to the Fc group through the organic adlayer. We argue that for the three short FcNs, the first process represents the rate-limiting step. The increase of the length of the alkyl chain leads to an approach of the Fc group to the STM tip, and consequently accelerates the first El' step. In case of the Fcl 1 junctions the rather high thickness of the organic layer leads to a decrease of the rate of the second ET step. In consequence, the contribution of the redox-mediated current enhancement to the total tunneling current appears to be insignificant. Our work demonstrates the importance of combined structural and transport approaches for the understanding of Er processes in electrochemical nanosystems. (C) 2010 Elsevier B.V. All rights reserved.

The electronic origin of contrast reversal in bias-dependent STM images of nanolines

Self-organized Bi lines that are only 1.5 nm wide can be grown without kinks or breaks on Si(0 0 1) surfaces to lengths of up to 500 nm. Constant-current topographical images of the lines, obtained with the scanning tunneling microscope, have a striking bias dependence. Although the lines appear darker than the Si terraces at biases below ≈∣1.2∣ V, the contrast reverses at biases above ≈∣1.5∣ V. Between these two ranges the lines and terraces are of comparable brightness. It has been suggested that this bias dependence may be due to the presence of a semiconductor-like energy gap within the line. Using ab initio calculations it is demonstrated that the energy gap is too small to explain the experimentally observed bias dependence. Consequently, at this time, there is no compelling explanation for this phenomenon. An alternative explanation is proposed that arises naturally from calculations of the tunneling current, using the Tersoff–Hamann approximation, and an examination of the electronic structure of the line.

Confined LO-phonon-assisted magnetotunneling in a parabolic quantum well with double barriers

The confined longitudinal-optical phonon-assisted tunneling through a parabolic quantum well with double barriers in a magnetic field perpendicular to the interfaces is studied theoretically based on a dielectric continuum model. The numerical results show that the applied magnetic field sharpens and heightens the phonon-assisted tunneling peaks in agreement with experimental observation. Furthermore, the phonon-assisted magnetotunneling peaks shift towards the higher biases as the magnetic field increases. In contrast to the results for a rectangular quantum well, the ratio of peak to valley of the phonon-assisted tunneling is larger for the wider well case. It also indicates that the phonon-assisted tunneling current peaks can be easily observed for a wider parabolic quantum well. (C) 2008 Published by Elsevier B.V.

Fabrication and transport properties of ZnO/Nb-1 wt %-doped SrTiO3 epitaxial heterojunctions

(110) ZnO/(001) Nb-1 wt %-doped SrTiO3 n-n type heteroepitaxial junctions were fabricated using the pulse laser deposition method. A diodelike current behavior was observed. Different from conventional p-n junctions or Schottky diodes, the diffusion voltage was found to increase with temperature. At all temperatures, the forward current was perfectly fitted on the thermionic emission model. The band bending at the interface can qualitatively explain our results, and the extracted high ideality factor at low temperatures, as well as large saturation currents, is ascribed to the deep-level-assisted tunneling current through the junction. (C) 2008 American Institute of Physics.

Quantum mechanical simulation of nanosized metal-oxide-semiconductor field-effect transistor using empirical pseudopotentials: A comparison for charge density occupation methods

The atomistic pseudopotential quantum mechanical calculations are used to study the transport in million atom nanosized metal-oxide-semiconductor field-effect transistors. In the charge self-consistent calculation, the quantum mechanical eigenstates of closed systems instead of scattering states of open systems are calculated. The question of how to use these eigenstates to simulate a nonequilibrium system, and how to calculate the electric currents, is addressed. Two methods to occupy the electron eigenstates to yield the charge density in a nonequilibrium condition are tested and compared. One is a partition method and another is a quasi-Fermi level method. Two methods are also used to evaluate the current: one uses the ballistic and tunneling current approximation, another uses the drift-diffusion method. (C) 2009 American Institute of Physics. [doi:10.1063/1.3248262]

Study on the reverse characteristics of Ti/6H-SiC Schottky contacts

The reverse I(V) measurement and analytic calculation of the electron transport across a Ti/6H-SiC Schottky barrier are presented. Based on the consideration of the barrier fluctuations and the barrier height shift caused by image charge and the applied voltage drop across Ti/SiC interfical layer, a comprehensive analytical model for the reverse tunneling current is developed using a WKB calculation of the tunneling probability through a reverse biased Schottky barrier. This model takes into account the main reverse conduction mechanism, such as field emission, thermionic field emission and thermionic emission. The fact that the simulated results are in good agreement with the experimental data indicates that the barrier height shift and barrier fluctuation can lead to reverse current densities orders of magnitude higher than that obtained from a simple theory. It is shown that the field and thermionic field emission processes, in which carries can tunnel through the barrier but cannot surmount it with insufficient thermal energy, dominate the reverse characteristics of a SiC Schottky contacts in a normal working condition.

Write-Once Read-Many-Times Memory Based on a Single Layer of Pentacene

We realized an organic electrical memory device with a simple structure based on single-layer pentacene film embedded between Al and ITO electrodes. The optimization of the thickness and deposition rate of pentacene resulted in a reliable device with an on/off current ratio as high as nearly 10(6), which was two orders of magnitude higher than previous results, and the storage time was more than 576 h. The current transition process is attributed to the formation and damage of the Interface dipole at different electric fields, in which the current conduction showed a transition from ohmic conductive current to Fowler-Nordheim tunneling current. After the transition from ON- to OFF-state, the device tended to remain in the OFF-State even when the applied voltage was removed, which indicated that the device was very promising for write-once read-many-times memory.

Molecular sensing with the tunnel junction of an Au nanogap in solution

The tunnel junction of a gold nanogap was fabricated electrochemically for a molecular sensing device in solution. The tunnel junction was sensitive enough to detect the variation of a potential barrier within the nanogap, such as the chemical adsorption of molecules. By monitoring the variation of the tunneling current, which represents the change of a potential barrier due to molecular adsorption, the molecules could be detected.

Quantum conductance of multiwall carbon nanotubes

An analysis on the conductance of multiwall carbon nanotubes (MWNT's) is presented. Recent experiment indicated that MWNT's are good quantum conductors. Our theory shows that tunneling current between states on different walls of a defect-free, infinitely long MWNT is vanishingly small in general, which leads to the quantization of the conductance of the MWNT's. With a reasonable simple model, we explicitly show that the conductance of a capped MWNT can be determined by the outermost wall for an infinitely long nanotube. We apply the theory to finite MWNT's and estimate the generic interwall conductance to be negligible compared to the intrawall ballistic conductance.

Temperature-dependent gap edge in strong-coupling superconductors determined using the Eliashberg-Nambu formalism

Using the theory of Eliashberg and Nambu for strong-coupling superconductors, we have calculated the gap function for a model superconductor and a selection of real superconductors includong the elements Al, Sn, Tl, Nb, In, Pb and Hg and one alloy, Bi2Tl. We have determined thetemperature-dependent gap edge in each and found that in materials with weak electron-phonon ($\lambda 1.20$), not only is the gap edge double valued but it also departs significantly from the BCS form and develops a shoulderlike structure which may, in some cases, denote a gap edge exceeding the $T = 0$ value. These computational results support the insights obtained by Leavens in an analytic consideration of the general problem. Both the shoulder and double value arise from a common origin seated in the form of the gap function in strong coupled materials at finite temperatures. From the calculated gap function, we can determine the densities of states in the materials and the form of the tunneling current-voltage characteristics for junctions with these materials as electroddes. By way of illustration, results are shown for the contrasting cases of Sn ($\lambda=0.74$) and Hg ($\lambad=1.63$). The reported results are distinct in several ways from BCS predictions and provide an incentive determinative experimental studies with techniques such as tunneling and far infrared absorption.

Multiphysics Simulation of Nanostructured Semiconductor Devices

Thesis (Ph.D.)--University of Washington, 2013

Spinpolarisierte Rastertunnelmikroskopie magnetischer Nanostrukturen am Beispiel von bcc-Co/Fe(110), Fe/Mo(110) und Kupfer-Phthalocyanin/Fe(110)

In dieser Arbeit werden, nach einer Einführung in die spinpolarisierte Rastertunnelmikroskopie und -spektroskopie als experimentelle Methode zur Untersuchung magnetischer Nanostrukturen, Ergebnisse zur spinpolarisierten elektronischen Struktur in Abhängigkeit von der Kristallstruktur am Beispiel ultradünner Co-Schichten sowie in Abhängigkeit von der Magnetisierungsrichtung für ultradünne Fe-Schichten vorgestellt. Hochaufgelöste Messungen zeigen die ortsabhängige Spinpolarisation auf einem einzelnen Kupfer-Phthalocyanin Molekül. rnrnKobalt wurde durch pseudomorphes Wachstum auf den (110)-Oberflächen der kubisch raumzentrierten Metalle Chrom und Eisen deponiert. Im Unterschied zu früheren Berichten in der Literatur lassen sich nur zwei Lagen Co in der kubisch raumzentrierten (bcc) Ordnung stabilisieren. Die bcc-Co Schichten auf der Fe(110)-Oberfläche zeigen keine Anzeichen von epitaktischen Verzerrungen. rnDickere Schichten rekonstruieren in eine dicht gepackte Struktur (hcp/fcc). Durch die bcc Ordnung wird die Spinpolarisation von Kobalt auf P=62% erhöht (hcp-Co: P=45%). rnrnDie temperaturabhängige Spinreorientierung (SRT) ultradünner Filme Fe/Mo(110) wurde mit spinpolarisierter Spektroskopie untersucht. Eine Neuausrichtung der Magnetisierung aus der senkrechten [110]-Achse in die in der Ebene liegenden [001]-Achse wird bei T=(13,2+-0,5)K festgestellt, wobei es sich um einen diskontinuierlichen Reorientierungsübergang handelt, d.h. die freie Energie weist innerhalb eines bestimmten Temperaturbereichs gleichzeitig zwei Minima auf. Weiterhin wird in der Mono- und Doppellage Fe/Mo(110 eine Abhängigkeit der elektronischen Struktur von der Ausrichtung der magnetisch leichten Achse und von der Magnetisierung beobachtet. rnrnDie Untersuchung des spinpolarisierten Ladungstransports durch ein Kupfer-Phthalocyanin-Molekül auf der Fe/Mo(110) Oberfläche liefert einen wesentlichen Beitrag zum Verständnis des Spintransports an der Grenzfläche zwischen Metall und organischem Molekül. Die HOMO-LUMO-Energielücke des freien Moleküls wird durch die Wechselwirkung mit der Metalloberfläche mit Grenzflächenzuständen gefüllt. Diese Zustände reduzieren die Spinpolarisation des durch das Molekül fließenden Tunnelstroms durch einen zusätzlichen unpolarisierten Strombeitrag um einen Faktor zwei. Spinpolarisierte hybridisierte Grenzflächenzustände mit größerem Abstand zur Fermi-Energie führen in Abhängigkeit von der Position auf dem Molekül zu weiteren Beiträgen zur effektiven Spinpolarisation. Diese Untersuchungen belegen die Möglichkeit einer effektiven Spininjektion in organische Halbleiter und damit das Potential dieser Materialien für die weitere Entwicklung von Spintronik-Bauteilen.

Charge and spin transport in nanoscale junction from first principles

Recently nanoscale junctions consisting of 0-D nanostructures (single molecule) or 1-D nanostructures (semiconducting nanowire) sandwiched between two metal electrodes are successfully fabricated and characterized. What lacks in the recent developments is the understanding of the mechanism behind the observed phenomena at the level of atoms and electrons. For example, the origin of observed switching effect in a semiconducting nanowire due to the influence of an external gate bias is not yet understood at the electronic structure level. On the same context, different experimental groups have reported different signs in tunneling magneto-resistance for the same organic spin valve structure, which has baffled researchers working in this field. In this thesis, we present the answers to some of these subtle questions by investigating the charge and spin transport in different nanoscale junctions. A parameter-free, single particle Green’s function approach in conjunction with a posteriori density functional theory (DFT) involving a hybrid orbital dependent functional is used to calculate the tunneling current in the coherent transport limit. The effect of spin polarization is explicitly incorporated to investigate spin transport in a nanoscale junction. Through the electron transport studies in PbS nanowire junction, a new orbital controlled mechanism behind the switching of the current is proposed. It can explain the switching behavior, not only in PbS nanowire, but in other lead-chalcogenide nanowires as well. Beside this, the electronic structure properties of this nanowire are studied using periodic DFT. The quantum confinement effect was investigated by calculating the bandgap of PbS nanowires with different diameters. Subsequently, we explain an observed semiconducting to metallic phase transition of this nanowire by calculating the bandgap of the nanowire under uniform radial strain. The compressive radial strain on the nanowire was found to be responsible for the metallic to semiconducting phase transition. Apart from studying one dimensional nanostructure, we also present transport properties in zero dimensional single molecular junctions. We proposed a new codoping approach in a single molecular carborane junction, where a cation and an anion are simultaneously doped to find the role of a single atom in the device. The main purpose was to build a molecular junction where a single atom can dictate the flow of electrons in a circuit. Recent observations of both positive and negative sign in tunneling magnetoresistance (TMR) the using same organic spin-valve structure hasmystified researchers. From our spin dependent transport studies in a prototypical organic molecular tunneling device, we found that a 3% change in metal-molecule interfacial distance can alter the sign of TMR. Changing the interfacial distance by 3%, the number of participating eigenstates as well as their orbital characteristic changes for anti-parallel configuration of the magnetization at the two electrodes, leading to the sign reversal of the TMR. Apart from this, the magnetic proximity effect under applied bias is investigated quantitatively, which can be used to understand the observed unexpectedmagnetismin carbon basedmaterials when they are in close proximity with magnetic substrates.

Resolving Atomic Connectivity in Graphene Nanostructure Junctions

We report on the structural characterization of junctions between atomically well-defined graphene nanoribbons (GNRs) by means of low-temperature, noncontact scanning probe microscopy. We show that the combination of simultaneously acquired frequency shift and tunneling current maps with tight binding (TB) simulations allows a comprehensive characterization of the atomic connectivity in the GNR junctions. The proposed approach can be generally applied to the investigation of graphene nanomaterials and their interconnections and is thus expected to become an important tool in the development of graphene-based circuitry.

Highly conductive p++-AlGaAs/n ++-GaInP tunnel junctions for ultra-high concentrator solar cells

Tunnel junctions are key for developing multijunction solar cells (MJSC) for ultra-high concentration applications. We have developed a highly conductive, high bandgap p  + + -AlGaAs/n  + + -GaInP tunnel junction with a peak tunneling current density for as-grown and thermal annealed devices of 996 A/cm 2 and 235 A/cm 2, respectively. The J–V characteristics of the tunnel junction after thermal annealing, together with its behavior at MJSCs typical operation temperatures, indicate that this tunnel junction is a suitable candidate for ultra-high concentrator MJSC designs. The benefits of the optical transparency are also assessed for a lattice-matched GaInP/GaInAs/Ge triple junction solar cell, yielding a current density increase in the middle cell of 0.506 mA/cm 2 with respect to previous designs.