STOCHASTIC CHARGE TRANSPORT IN MULTI-ISLAND SINGLE-ELECTRON TUNNELING DEVICES

The physics of the operation of singe-electron tunneling devices (SEDs) and singe-electron tunneling transistors (SETs), especially of those with multiple nanometer-sized islands, has remained poorly understood in spite of some intensive experimental and theoretical research. This computational study examines the current-voltage (IV) characteristics of multi-island single-electron devices using a newly developed multi-island transport simulator (MITS) that is based on semi-classical tunneling theory and kinetic Monte Carlo simulation. The dependence of device characteristics on physical device parameters is explored, and the physical mechanisms that lead to the Coulomb blockade (CB) and Coulomb staircase (CS) characteristics are proposed. Simulations using MITS demonstrate that the overall IV characteristics in a device with a random distribution of islands are a result of a complex interplay among those factors that affect the tunneling rates that are fixed a priori (e.g. island sizes, island separations, temperature, gate bias, etc.), and the evolving charge state of the system, which changes as the source-drain bias (VSD) is changed. With increasing VSD, a multi-island device has to overcome multiple discrete energy barriers (up-steps) before it reaches the threshold voltage (Vth). Beyond Vth, current flow is rate-limited by slow junctions, which leads to the CS structures in the IV characteristic. Each step in the CS is characterized by a unique distribution of island charges with an associated distribution of tunneling probabilities. MITS simulation studies done on one-dimensional (1D) disordered chains show that longer chains are better suited for switching applications as Vth increases with increasing chain length. They are also able to retain CS structures at higher temperatures better than shorter chains. In sufficiently disordered 2D systems, we demonstrate that there may exist a dominant conducting path (DCP) for conduction, which makes the 2D device behave as a quasi-1D device. The existence of a DCP is sensitive to the device structure, but is robust with respect to changes in temperature, gate bias, and VSD. A side gate in 1D and 2D systems can effectively control Vth. We argue that devices with smaller island sizes and narrower junctions may be better suited for practical applications, especially at room temperature.

Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy

The electronic structure of atomically precise armchair graphene nanoribbons of width N=7 (7-AGNRs) are investigated by scanning tunneling spectroscopy (STS) on Au(111). We record the standing waves in the local density of states of finite ribbons as a function of sample bias and extract the dispersion relation of frontier electronic states by Fourier transformation. The wave-vector-dependent contributions from these states agree with density functional theory calculations, thus enabling the unambiguous assignment of the states to the valence band, the conduction band, and the next empty band with effective masses of 0.41±0.08me,0.40±0.18me, and 0.20±0.03me, respectively. By comparing the extracted dispersion relation for the conduction band to corresponding height-dependent tunneling spectra, we find that the conduction band edge can be resolved only at small tip-sample separations and has not been observed before. As a result, we report a band gap of 2.37±0.06 eV for 7-AGNRs adsorbed on Au(111).

Electron tunneling in protein crystals

The current understanding of electron tunneling through proteins has come from work on systems where donors and acceptors are held at fixed distances and orientations. The factors that control electron flow between proteins are less well understood, owing to uncertainties in the relative orientations and structures of the reactants during the very short time that tunneling occurs. As we report here, the way around such structural ambiguity is to examine oxidation–reduction reactions in protein crystals. Accordingly, we have measured and analyzed the kinetics of electron transfer between native and Zn-substituted tuna cytochrome c (cyt c) molecules in crystals of known structure. Electron transfer rates [(320 s−1 for *Zn-cyt c → Fe(III)-cyt c; 2000 s−1 for Fe(II)-cyt c → Zn-cyt c+)] over a Zn–Fe distance of 24.1 Å closely match those for intraprotein electron tunneling over similar donor–acceptor separations. Our results indicate that van der Waals interactions and water-mediated hydrogen bonds are effective coupling elements for tunneling across a protein–protein interface.

Imaging of spin waves in atomically designed nanomagnets

The spin dynamics of all ferromagnetic materials are governed by two types of collective phenomenon: spin waves and domain walls. The fundamental processes underlying these collective modes, such as exchange interactions and magnetic anisotropy, all originate at the atomic scale. However, conventional probing techniques based on neutron1 and photon scattering2 provide high resolution in reciprocal space, and thereby poor spatial resolution. Here we present direct imaging of standing spin waves in individual chains of ferromagnetically coupled S = 2 Fe atoms, assembled one by one on a Cu2N surface using a scanning tunnelling microscope. We are able to map the spin dynamics of these designer nanomagnets with atomic resolution in two complementary ways. First, atom-to-atom variations of the amplitude of the quantized spin-wave excitations are probed using inelastic electron tunnelling spectroscopy. Second, we observe slow stochastic switching between two opposite magnetization states3, 4, whose rate varies strongly depending on the location of the tip along the chain. Our observations, combined with model calculations, reveal that switches of the chain are initiated by a spin-wave excited state that has its antinodes at the edges of the chain, followed by a domain wall shifting through the chain from one end to the other. This approach opens the way towards atomic-scale imaging of other types of spin excitation, such as spinon pairs and fractional end-states5, 6, in engineered spin chains.

Biaxial strain induced electrical inhomogenities and phase separation in the ferromagnetic metallic phase in thin films of La0.7Ca0.3MnO3: A scanning tunneling potentiometry/spectroscopy study

We have investigated the effect of biaxial strain on local electrical/electronic properties in thin films of La0.7Ca0.3MnO3 with varying degrees of biaxial strain in them. The local electrical properties were investigated as a function of temperature by scanning tunneling spectroscopy (STS) and scanning tunneling potentiometry (STP), along with the bulk probe like conductance fluctuations.The results indicate a positive correlation between the lattice mismatch biaxial strain and the local electrical/electronic inhomogenities observed in the strained sample. This is plausible since the crystal structure of the manganites interfere rather strongly with the magnetic/electronic degrees of freedom. Thus even a small imbalance (biaxial strain) can induce significant changes in the electrical properties of the system.

Scanning tunneling spectroscopic studies on high-temperature superconductors and Dirac materials

This thesis details the investigations of the unconventional low-energy quasiparticle excitations in electron-type cuprate superconductors and electron-type ferrous superconductors as well as the electronic properties of Dirac fermions in graphene and three-dimensional strong topological insulators through experimental studies using spatially resolved scanning tunneling spectroscopy (STS) experiments.

Magnetic-field- and temperature-dependent evolution of the spatially resolved quasiparticle spectra in the electron-type cuprate La_0.1Sr_0.9CuO₂ (La-112) T_C = 43 K, are investigated experimentally. For temperature (T) less than the superconducting transition temperature (TC), and in zero field, the quasiparticle spectra of La-112 exhibits gapped behavior with two coherence peaks and no satellite features. For magnetic field measurements at T < TC, first ever observation of vortices in La-112 are reported. Moreover, pseudogap-like spectra are revealed inside the core of vortices, where superconductivity is suppressed. The intra-vortex pseudogap-like spectra are characterized by an energy gap of V_PG = 8.5 ± 0.6 meV, while the inter-vortex quasiparticle spectra shows larger peak-to-peak gap values characterized by Δ_pk-pk(H) >V_PG, and Δ_pk-pk (0)=12.2 ± 0.8 meV > Δ_pk-pk (H > 0). The quasiparticle spectra are found to be gapped at all locations up to the highest magnetic field examined (H = 6T) and reveal an apparent low-energy cutoff at the V_PG energy scale.

Magnetic-field- and temperature-dependent evolution of the spatially resolved quasiparticle spectra in the electron-type "122" iron-based Ba(Fe_1-xCo_x)₂A_s2 are investigated for multiple doping levels (x = 0.06, 0.08, 0.12 with T_C= 14 K, 24 K, and 20 K). For all doping levels and the T < T_C, two-gap superconductivity is observed. Both superconducting gaps decrease monotonically in size with increasing temperature and disappear for temperatures above the superconducting transition temperature, T_C. Magnetic resonant modes that follow the temperature dependence of the superconducting gaps have been identified in the tunneling quasiparticle spectra. Together with quasiparticle interference (QPI) analysis and magnetic field studies, this provides strong evidence for two-gap sign-changing s-wave superconductivity.

Additionally spatial scanning tunneling spectroscopic studies are performed on mechanically exfoliated graphene and chemical vapor deposition grown graphene. In all cases lattice strain exerts a strong influence on the electronic properties of the sample. In particular topological defects give rise to pseudomagnetic fields (B ~ 50 Tesla) and charging effects resulting in quantized conductance peaks associated with the integer and fractional Quantum Hall States.

Finally, spectroscopic studies on the 3D-STI, Bi₂Se₃ found evidence of impurity resonance in the surface state. The impurities are in the unitary limit and the spectral resonances are localized spatially to within ~ 0.2 nm of the impurity. The spectral weight of the impurity resonance diverges as the Fermi energy approaches the Dirac point and the rapid recovery of the surface state suggests robust topological protection against perturbations that preserve time reversal symmetry.

Capturing protein dynamics with time-resolved luminescence spectroscopy

The presented doctoral research utilizes time-resolved spectroscopy to characterize protein dynamics and folding mechanisms. We resolve millisecond-timescale folding by coupling time-resolved fluorescence energy transfer (trFRET) to a continuous flow microfluidic mixer to obtain intramolecular distance distributions throughout the folding process. We have elucidated the folding mechanisms of two cytochromes---one that exhibits two-state folding (cytochrome cb₅₆₂) and one that has both a kinetic refolding intermediate ensemble and a distinct equilibrium unfolding intermediate (cytochrome c₅₅₂). Our data reveal that the distinct structural features of cytochrome c₅₅₂ contribute to its thermostability.

We have also investigated intrachain contact dynamics in unfolded cytochrome cb₅₆₂ by monitoring electron transfer, which occurs as the heme collides with a ruthenium photosensitizer, covalently bound to residues along the polypeptide. Intrachain diffusion for chemically denatured proteins proceeds on the microsecond timescale with an upper limit of 0.1 microseconds. The power-law dependence (slope = -1.5) of the rate constants on the number of peptide bonds between the heme and Ru complex indicate that cytochrome cb₅₆₂ is minimally frustrated.

In addition, we have explored the pathway dependence of electron tunneling rates between metal sites in proteins. Our research group has converted cytochrome b₅₆₂ to a c-type cytochrome with the porphyrin covalently bound to cysteine sidechains. We have investigated the effects of the changes to the protein structure (i.e., increased rigidity and potential new equatorial tunneling pathways) on the electron transfer rates, measured by transient absorption, in a series of ruthenium photosensitizer-modified proteins.

Correlated electron-ion dynamics: the excitation of atomic motion by energetic electrons

Correlated electron-ion dynamics (CEID) is an extension of molecular dynamics that allows us to introduce in a correct manner the exchange of energy between electrons and ions. The formalism is based on a systematic approximation: small amplitude moment expansion. This formalism is extended here to include the explicit quantum spread of the ions and a generalization of the Hartree-Fock approximation for incoherent sums of Slater determinants. We demonstrate that the resultant dynamical equations reproduce analytically the selection rules for inelastic electron-phonon scattering from perturbation theory, which control the mutually driven excitations of the two interacting subsystems. We then use CEID to make direct numerical simulations of inelastic current-voltage spectroscopy in atomic wires, and to exhibit the crossover from ionic cooling to heating as a function of the relative degree of excitation of the electronic and ionic subsystems.

High-resolution electron energy-loss spectroscopy of Ba Ti O 3∕ Sr Ti O 3 multilayers

The dielectric properties of BaTiO3 thin films and multilayers are different from bulk materials because of nanoscale dimensions, interfaces, and stress-strain conditions. In this study, BaTiO3/SrTiO3 multilayers deposited on SrTiO3 substrates by pulsed laser deposition have been investigated by high-energy-resolution electron energy-loss spectroscopy. The fine structures in the spectra are discussed in terms of crystal-field splitting and the internal strain. The crystal-field splitting of the BaTiO3 thin layer is found to be a little larger than that of bulk BaTiO3, which has been interpreted by the presence of the internal strain induced by the misfit at the interface. This finding is consistent with the lattice parameters of the BaTiO3 thin layer determined by the selected area diffraction pattern. The near-edge structure of the oxygen K edge in BaTiO3 thin layers and in bulk BaTiO3 are simulated by first-principle self-consistent full multiple-scattering calculations. The results of the simulations are in a good agreement with the experimental results. Moreover, the aggregation of oxygen vacancies at the rough BaTiO3/SrTiO3 interface is indicated by the increased [Ti]/[O] element ratio, which dominates the difference of dielectric properties between BaTiO3 layer and bulk materials.

Tunnelkontakte mit Heusler-Elektrode: Spinpolarisation von Co 2Cr 0,6Fe 0,4Al und Einfluss der Barriere

Ziel dieser Arbeit ist die Bestimmung der Spinpolarisation von der Heusler-Verbindung Co2Cr0,6Fe0,4Al. Dieses Ziel wurde durch die sorgfältige Präparation von Co2Cr0,6Fe0,4Al basierten Tunnelkontakten realisiert. Tunnelwiderstandsmessungen an Co2Cr0,6Fe0,4Al-basiertenrnTunnelkontakten ergaben einen Tunnelmagnetowiderstand von 101% bei 4 K. DieserrnTunnelmagnetowiderstand legt eine untere Grenze von 67% für die Spinpolarisation von Co2Cr0,6Fe0,4Al fest.rnrnCo2Cr0,6Fe0,4Al ist eine Heusler-Verbindung, der die Eigenschaften eines halbmetallischen Ferromagneten zugeschrieben werden. Ein halbmetallischer Ferromagnet hat an der Fermikante nur Elektronenspinzustände mit einer Polarisation. Als Folge davon können bei einem spinerhaltenden Tunnelprozess nur Elektronen einer Spinrichtung in den halbmetallischen Ferromagneten tunneln. Mit einem magnetischen Feld und einer durch einen Antiferromagneten fixierten Gegenelektrode, können an einem Tunnelkontakt mit einem spinpolarisierten Ferromagneten deshalb zwei Zustände, eine hohe und eine niedrige Tunnelleitfähigkeit, erzeugt werden. Daher finden spinpolarisierte Tunnelkontakte in Form von MRAM in der Datenspeicherung Verwendung. Bislang wurde jedoch keine Verbindung gefunden, der eine Spinpolarisation von 100% experimentell eindeutig nachgewiesen werden konnte. Für Co2Cr0,6Fe0,4Al lagen die höchsten gemessenen Spinpolarisationen um 50%.rnrnTunnelspektroskopie ist eine zuverlässige und anwendungsnahe Methode zur Untersuchung der Spinpolarisation. Inelastische Tunnelprozesse und eine reduzierte Ordnung an Grenzflächen bewirken einen reduzierten Tunnelmagnetowiderstand. Eine symmetriebrechende Barriere, wie amorphes AlOx, ist Voraussetzung für die Anwendung des Jullière-Modells zur Bestimmung der Spinpolarisation. Das Jullière-Modell verknüpft die Spin-aufgespaltenenrnZustandsdichten der Elektroden mit dem Tunnelmagnetowiderstand. Ohne einernsymmetriebrechende Barriere, zum Beispiel mit MgO als Isolatorschicht, können höhere Tunnelmagnetowiderstände erzwungen werden. Ein eindeutiger Rückschluss auf die Spinpolarisation ist dann jedoch nicht mehr möglich. Mit Aluminiumoxid-basierten Barrieren liefert die Anwendung des einfachen Jullière-Modells eine Untergrenze der Spinpolarisation.rnrnUm die Spinpolarisation von Co2Cr0,6Fe0,4Al durch Tunnelspektroskopie zu bestimmen, musste die Präparation der Tunnelkontakte verbessert werden. Dies wurde ermöglicht durch den Anbau einer neuen Sputterkammer mit besseren UHV-Bedingungen an ein bestehendes Präparationscluster. Co2Cr0,6Fe0,4Al wird mit Hilfe von Radiofrequenz-Kathodenzerstäuben deponiert. Die resultierenden Schichten verfügen nach ihrer Deposition über einen höheren Ordnungsgrad und über eine geordnete Oberfläche. Durch eine Magnesium-Pufferschicht war es möglich, auf diese Oberfläche eine homogene amorphe AlOx-Barriere zu deponieren. Als Gegenelektrode wurde CoFe als Ferromagnet mit MnFe als Antiferromagnet gewählt. Diese Gegenelektrode ermöglicht Tunnelmessungen bis hin zu Raumtemperatur.rnrnMit den in dieser Arbeit vorgestellten optimierten Analyse- und Präparationsmethoden ist es möglich, die Untergrenze der Spinpolarisation von Co2Cr0,6Fe0,4Al auf 67% anzuheben. Dies ist der bisher höchste veröffentlichte Wert der Spinpolarisation von Co2Cr0,6Fe0,4Al.rn

MULTISCALE EXAMINATION AND MODELING OF ELECTRON TRANSPORT IN NANOSCALE MATERIALS AND DEVICES

For half a century the integrated circuits (ICs) that make up the heart of electronic devices have been steadily improving by shrinking at an exponential rate. However, as the current crop of ICs get smaller and the insulating layers involved become thinner, electrons leak through due to quantum mechanical tunneling. This is one of several issues which will bring an end to this incredible streak of exponential improvement of this type of transistor device, after which future improvements will have to come from employing fundamentally different transistor architecture rather than fine tuning and miniaturizing the metal-oxide-semiconductor field effect transistors (MOSFETs) in use today. Several new transistor designs, some designed and built here at Michigan Tech, involve electrons tunneling their way through arrays of nanoparticles. We use a multi-scale approach to model these devices and study their behavior. For investigating the tunneling characteristics of the individual junctions, we use a first-principles approach to model conduction between sub-nanometer gold particles. To estimate the change in energy due to the movement of individual electrons, we use the finite element method to calculate electrostatic capacitances. The kinetic Monte Carlo method allows us to use our knowledge of these details to simulate the dynamics of an entire device— sometimes consisting of hundreds of individual particles—and watch as a device ‘turns on’ and starts conducting an electric current. Scanning tunneling microscopy (STM) and the closely related scanning tunneling spectroscopy (STS) are a family of powerful experimental techniques that allow for the probing and imaging of surfaces and molecules at atomic resolution. However, interpretation of the results often requires comparison with theoretical and computational models. We have developed a new method for calculating STM topographs and STS spectra. This method combines an established method for approximating the geometric variation of the electronic density of states, with a modern method for calculating spin-dependent tunneling currents, offering a unique balance between accuracy and accessibility.

Microscopic and spectroscopic investigation of poly(3-hexylthiophene) interaction with carbon nanotubes

The inclusion of carbon nanotubes in polymer matrix has been proposed to enhance the polymer’s physical and electrical properties. In this study, microscopic and spectroscopic techniques are used to investigate the interaction between poly(3-hexylthiophene) (P3HT) and nanotubes and the reciprocal modification of physical properties. The presence of P3HT-covered nanotubes dispersed in the polymer matrix has been observed by atomic force microscopy and transmission electron microscopy. Then, the modification of P3HT optical properties due to nanotube inclusion has been evidenced with spectroscopic techniques like absorption and Raman spectroscopy. The study is completed with detailed nanoscale analysis by scanning probe techniques. The ordered self assembly of polymer adhering on the nanotube is unveiled by showing an example of helical wrapping of P3HT. Scanning tunneling spectroscopy study provides information on the electronic structure of nanotube-polymer assembly, revealing the charge transfer from P3HT to the nanotube.

Intermolecular Interactions of Noble-Gas-Containing Species

The importance of intermolecular interactions to chemistry, physics, and biology is difficult to overestimate. Without intermolecular forces, condensed phase matter could not form. The simplest way to categorize different types of intermolecular interactions is to describe them using van der Waals and hydrogen bonded (H-bonded) interactions. In the H-bond, the intermolecular interaction appears between a positively charged hydrogen atom and electronegative fragments and it originates from strong electrostatic interactions. H-bonding is important when considering the properties of condensed phase water and in many biological systems including the structure of DNA and proteins. Vibrational spectroscopy is a useful tool for studying complexes and the solvation of molecules. Vibrational frequency shift has been used to characterize complex formation. In an H-bonded system A∙∙∙H-X (A and X are acceptor and donor species, respectively), the vibrational frequency of the H-X stretching vibration usually decreases from its value in free H-X (red-shift). This frequency shift has been used as evidence for H-bond formation and the magnitude of the shift has been used as an indicator of the H-bonding strength. In contrast to this normal behavior are the blue-shifting H-bonds, in which the H-X vibrational frequency increases upon complex formation. In the last decade, there has been active discussion regarding these blue-shifting H-bonds. Noble-gases have been considered inert due to their limited reactivity with other elements. In the early 1930 s, Pauling predicted the stable noble-gas compounds XeF6 and KrF6. It was not until three decades later Neil Bartlett synthesized the first noble-gas compound, XePtF6, in 1962. A renaissance of noble-gas chemistry began in 1995 with the discovery of noble-gas hydride molecules at the University of Helsinki. The first hydrides were HXeCl, HXeBr, HXeI, HKrCl, and HXeH. These molecules have the general formula of HNgY, where H is a hydrogen atom, Ng is a noble-gas atom (Ar, Kr, or Xe), and Y is an electronegative fragment. At present, this class of molecules comprises 23 members including both inorganic and organic compounds. The first and only argon-containing neutral chemical compound HArF was synthesized in 2000 and its properties have since been investigated in a number of studies. A helium-containing chemical compound, HHeF, was predicted computationally, but its lifetime has been predicted to be severely limited by hydrogen tunneling. Helium and neon are the only elements in the periodic table that do not form neutral, ground state molecules. A noble-gas matrix is a useful medium in which to study unstable and reactive species including ions. A solvated proton forms a centrosymmetric NgHNg+ (Ng = Ar, Kr, and Xe) structure in a noble-gas matrix and this is probably the simplest example of a solvated proton. Interestingly, the hypothetical NeHNe+ cation is isoelectronic with the water-solvated proton H5O2+ (Zundel-ion). In addition to the NgHNg+ cations, the isoelectronic YHY- (Y = halogen atom or pseudohalogen fragment) anions have been studied with the matrix-isolation technique. These species have been known to exist in alkali metal salts (YHY)-M+ (M = alkali metal e.g. K or Na) for more than 80 years. Hydrated HF forms the FHF- structure in aqueous solutions, and these ions participate in several important chemical processes. In this thesis, studies of the intermolecular interactions of HNgY molecules and centrosymmetric ions with various species are presented. The HNgY complexes show unusual spectral features, e.g. large blue-shifts of the H-Ng stretching vibration upon complexation. It is suggested that the blue-shift is a normal effect for these molecules, and that originates from the enhanced (HNg)+Y- ion-pair character upon complexation. It is also found that the HNgY molecules are energetically stabilized in the complexed form, and this effect is computationally demonstrated for the HHeF molecule. The NgHNg+ and YHY- ions also show blue-shifts in their asymmetric stretching vibration upon complexation with nitrogen. Additionally, the matrix site structure and hindered rotation (libration) of the HNgY molecules were studied. The librational motion is a much-discussed solid state phenomenon, and the HNgY molecules embedded in noble-gas matrices are good model systems to study this effect. The formation mechanisms of the HNgY molecules and the decay mechanism of NgHNg+ cations are discussed. A new electron tunneling model for the decay of NgHNg+ absorptions in noble-gas matrices is proposed. Studies of the NgHNg+∙∙∙N2 complexes support this electron tunneling mechanism.