Temperatur- und ortsabhängige Zustandsdichte des organischen Supraleiters Kappa-(BEDT-TTF) 2 Cu[N(CN) 2]Br

Im Rahmen dieser Arbeit wurde die temperatur- und ortsabhängige Zustandsdichte des organischen Supraleiters kappa-(BEDT-TTF)2Cu[N(CN)2]Br mit Rastertunnelspektroskopie bei tiefen Temperaturen untersucht.rnZusätzlich zur bereits bekannten supraleitenden Energielücke wird dabei eine logarithmische Unterdrückung der Zustandsdichte an der Fermikante beobachtet, die auch oberhalb der kritischen Temperatur erhalten bleibt. In der vorliegenden Arbeit wird gezeigt, dass sich dieses Verhalten durch ein für ungeordnete elektronische Systeme entwickeltes Modell unter Berücksichtigung von Coulomb-Wechselwirkungen beschreiben lässt. Die daraus resultierenden Fluktuationen der elektronischen Struktur führen zu einer Verbreiterung der gemessenen supraleitenden Energielücke, die sich durch sehr kleine Kohärenzmaxima im entsprechenden Quasiteilchenanregungsspektrum äußert. Dieses Verhalten wurde bereits beobachtet, konnte jedoch bisher nicht erklärt werden. Die theoretische Beschreibung der logarithmischen Unterdrückung trägt somit zusätzlich zum Verständnis des supraleitenden Beitrags bei, sodass die gesamte Zustandsdichte vollständig beschrieben werden kann. Die Analyse der gemessenen supraleitenden Energielücke wurde für verschiedene Symmetrien des Ordnungsparameters durchgeführt, wobei die beste Übereinstimmung für die Annahme einer d-wellenartigen Symmetrie mit zwei unterschiedlich stark ausgeprägten Energielücken gefunden wurde. Der Paarbildungsmechanismus, der zur Bindung zweier Elektronen zu einem Cooper-Paar führt, kann mit einer $d$-wellenartigen Symmetrie nicht durch die in konventionellen Supraleitern gefundene Elektron-Phonon-Kopplung erklärt werden. Stattdessen wird in Analogie zur Hochtemperatur-Supraleitung eine durch antiferromagnetische Spin-Wechselwirkungen induzierte Kopplung der Elektronen vermutet. Dies wird zum einen durch die oberhalb der kritischen Temperatur auftretende, zweite Energielücke und zum anderen durch die zwischen 4,66 und 5,28 liegende Kopplungsstärke 2Delta/(kB Tc) unterstützt, die deutlich größer als für konventionelle Supraleiter mit Elektron-Phonon-Kopplung ist.

Highly-effective gating of single-molecule junctions: an electrochemical approach

We report an electrochemical gating approach with [similar]100% efficiency to tune the conductance of single-molecule 4,4′-bipyridine junctions using scanning-tunnelling-microscopy break junction technique. Density functional theory calculation suggests that electrochemical gating aligns molecular frontier orbitals relative to the electrode Fermi-level, switching the molecule from an off resonance state to “partial” resonance.

Application of photoluminescence and electroluminescence techniques to the characterization of intermediate band solar cells

The intermediatebandsolarcell (IBSC) is a photovoltaic device with a theoretical conversion efficiency limit of 63.2%. In recent years many attempts have been made to fabricate an intermediateband material which behaves as the theory states. One characteristic feature of an IBSC is its luminescence spectrum. In this work the temperature dependence of the photoluminescence (PL) and electroluminescence (EL) spectra of InAs/GaAs QD-IBSCs together with their reference cell have been studied. It is shown that EL measurements provide more reliable information about the behaviour of the IB material inside the IBSC structure than PL measurements. At low temperatures, the EL spectra are consistent with the quasi-Fermi level splits described by the IBSC model, whereas at room temperature they are not. This result is in agreement with previously reported analysis of the quantum efficiency of the solarcells

Nanotechnology for more efficient photovoltaics: the quantum dot intermediate band solar cell

The intermediate band solar cell [1] has been proposed as a concept able to substantially enhance the efficiency limit of an ordinary single junction solar cell. If a band permitted for electrons is inserted within the forbidden band of a semiconductor then a novel path for photo generation is open: electron hole pairs may be formed by the successive absorption of two sub band gap photons using the intermediate band (IB) as a stepping stone. While the increase of the photovoltaic (PV) current is not a big achievement —it suffices to reduce the band gap— the achievement of this extra current at high voltage is the key of the IB concept. In ordinary cells the voltage is limited by the band gap so that reducing it would also reduce the band gap. In the intermediate band solar cell the high voltage is produced when the IB is permitted to have a Quasi Fermi Level (QFL) different from those of the Conduction Band (CB) and the Valence Band (VB). For it the cell must be properly isolated from the external contacts, which is achieved by putting the IB material between two n- and p-type ordinary semiconductors [2]. Efficiency thermodynamic limit of 63% is obtained for the IB solar cell1 vs. the 40% obtained [3] for ordinary single junction solar cells. Detailed information about the IB solar cells can be found elsewhere [4].

Thermally assisted tunneling transport in La0.7Ca0.3MnO3/SrTiO3:Nb Schottky-like heterojunctions

We report on the electrical transport properties of all-oxide La0.7Ca0.3MnO3/SrTiO3:Nb heterojunctions with lateral size of just a few micrometers. The use of lithography techniques to pattern manganite pillars ensures perpendicular transport and allows exploration of the microscopic conduction mechanism through the interface. From the analysis of the current-voltage characteristics in the temperature range 20-280 K we find a Schottky-like behavior that can be described by a mechanism of thermally assisted tunneling if a temperature-dependent value of the dielectric permittivity of SrTiO3:Nb (NSTO) is considered.We determine the Schottky energy barrier at the interface, qVB = 1.10 ± 0.02 eV, which is found to be temperature independent, and a value of ? = 17 ± 2 meV for the energy of the Fermi level in NSTO with respect to the bottom of its conduction band.

Supercondutividade em ligas de Ta1-xZrx

No presente estudo, amostras policristalinas ricas em Ta e com estequiometrias Ta1-xZrx; x < 0.15; foram preparadas através da mistura apropriada dos elementos metálicos, os quais foram fundidos em forno a arco elétrico sobre uma placa de cobre refrigerada a água e sob atmosfera de argônio de alta pureza. Os padrões de difração de raios-X das ligas, como fundidas (as cast) e tratadas termicamente a 850 °C por 24 h, revelaram a ocorrência de uma estrutura cristalina cúbica de corpo centrada bcc, tipo W, e parâmetros de rede que aumentam suavemente com o aumento do teor de Zr nas ligas. Medidas de susceptibilidade magnética dc, conduzidas nas condições de resfriamento da amostra em campo zero (ZFC) e do resfriamento com o campo magnético aplicado (FC), indicaram que supercondutividade volumétrica é observada abaixo de ~ 5.8, 6.9, 7.0 K em amostras com x = 0.05, 0.08, e 0.10, respectivamente. Essas temperaturas críticas supercondutoras são bastante superiores àquela observada no Ta elementar ~ 4.45 K. Medidas de resistividade elétrica na presença de campos magnéticos aplicados de até 9 T confirmaram a temperatura crítica supercondutora das amostras estudadas. O campo crítico superior Hc2 e o comprimento de coerência E foram estimados a partir dos dados de magnetorresistência. Os valores estimados de Hc2 foram de ~ 0.46, 1.78, 3.85 e 3.97 T, resultando em valores de E ~ 26.0, 13.6, 9.2 e 9.1 nm para as ligas as cast com x = 0.00, 0.05, 0.08 e 0.10, respectivamente. A partir dos dados experimentais do calor específico Cp das ligas, magnitudes estimadas do salto em Cp nas vizinhanças das transições supercondutoras indicaram valores maiores que o previsto pela teoria BCS. Utilizando as equações analíticas derivadas da teoria do acoplamento forte da supercondutividade foi então proposto que o aumento da temperatura de transição supercondutora nas ligas devido a substituição parcial do Ta por Zr está intimamente relacionado ao aumento do acoplamento elétron-fônon, visto que a densidade de estados eletrônicos no nível de Fermi foi estimada ser essencialmente constante através da série Ta1-xZrx com x < 0.10.

Transport across two interacting quantum dots: Bulk Kondo, Kondo box, and molecular regimes

We analyze the transport properties of a double quantum dot device with both dots coupled to perfect conducting leads and to a finite chain of N noninteracting sites connecting both of them. The interdot chain strongly influences the transport across the system and the local density of states of the dots. We study the case of a small number of sites, so that Kondo box effects are present, varying the coupling between the dots and the chain. For odd N and small coupling between the interdot chain and the dots, a state with two coexisting Kondo regimes develops: the bulk Kondo due to the quantum dots connected to leads and the one produced by the screening of the quantum dot spins by the spin in the finite chain at the Fermi level. As the coupling to the interdot chain increases, there is a crossover to a molecular Kondo effect, due to the screening of the molecule (formed by the finite chain and the quantum dots) spin by the leads. For even N the two Kondo temperatures regime does not develop and the physics is dominated by the usual competition between Kondo and antiferromagnetism between the quantum dots. We finally study how the transport properties are affected as N is increased. For the study we used exact multiconfigurational Lanczos calculations and finite-U slave-boson mean-field theory at T=0. The results obtained with both methods describe qualitatively and also quantitatively the same physics.

Competition between disorder and exchange splitting in superconducting ZrZn2

We propose a simple picture for the occurrence of superconductivity and the pressure dependence of the superconducting critical temperature, T-SC, in ZrZn2. According to our hypothesis the pairing potential is independent of pressure, but the exchange splitting, E-xc leads to a pressure dependence in the (spin dependent) density of states at the Fermi level, D-sigma (epsilon(F)). Assuming p-wave pairing T-SC is dependent on D-sigma (epsilonF) which ensures that, in the absence of non-magnetic impurities, T-SC decreases as pressure is applied until it reaches a minimum in the paramagnetic state. Disorder reduces this minimum to zero, this gives the illusion that the superconductivity disappears at the same pressure as ferromagnetism does.

A study of the electrical and optical properties of unhydrogenated neon-sputtered amorphous silicon

Films of amorphous silicon (a-Si) were prepared by r.f. sputtering in a Ne plasma without the addition of hydrogen or a halogen. The d.c. dark electrical conductivity, he optical gap and the photoconductivity of the films were investigated for a range of preparation conditions, the sputtering gas pressure, P, the target-substrate spacing, d, the self-bias voltage, Vsb, on the target and the substrate temperature, Ts. The dependence of the electrical and optical properties on these conditions showed that various combinations of P, d and Vsb, at a constant Ts, giving the same product (Pd/V sb) result in films with similar properties, provided that P, d and Vsb remain vithin a certain range. Variation of Pd/Vsb between about 0.2 and 0.8 rrTorr.cm!V varied the dark conductivity over about 4 orders of magnitude, the optical gap by 0.5 eV and the photoconductivity over 4-5 orders of magnitude. This is attributed to controlling the density-of-states distribution in the mobility gap. The temperature-dependence of photoconductivity and the photoresponse of undoped films are in support of this conclusion. Films prepared at relatively high (Pd/Vsb) values and Ts=300 ºc: exhibited low dark-conductivity and high thermal activation energy, optical gap and photoresponse, characteristic properties of a 'low density-of-states material. P-type doping with group-Ill elements (Al, B and Ga) by sputtering from a composite target or from a predoped target (B-.doped) was investigated. The systematic variation of room-temperature conductivity over many orders of magnitude and a Fermi-level shift of about 0.7 eV towards the valence-band edge suggest that substitutional doping had taken place. The effects of preparation conditions on doping efficiency were also investigated. The post-deposition annealing of undoped and doped films were studied for a temperature range from 250 ºC to 470 ºC. It was shown that annealing enhanced the doping efficiency considerably, although it had little effect on the basic material (a-Si) prepared at the optimum conditions (Pd/Vsb=0.8 mTorr.cm/V and Ts=300 $ºC). Preliminary experiments on devices imply potential applications of the present material, such as p-n and MS junctions.

Carbon nanostructure based electrodes for high efficiency dye sensitized solar cell

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

Interações magnéticas e elétricas em GaMnAs

In this paper, we will address together the magnetic and electrical properties of a particular semiconductor, the GaMnAs. The treatment will be done analytically in the first part of the work, according to the computational method for simulation of physical systems through the implementation of the expressions obtained in the first part. All study of magnetic contribution will be made using an interaction Kondo type, using an approach by Green functions. The electrical part, which consists of the Coulomb interactions between carriers and Mn ions, will be treated within the approach of multiple scattering. The implementation of the proposed method will calculate the Green functions converged as multiple scattering solution and use them as a starting point for the calculation of the effective magnetic interactions between Mn ions mediated charge carriers. The concentration parameters were varied for Mn ions and carriers as well. The combination of these two parameters can lead to insulating, metal samples with carriers in Fermi level to low or high mobility. As a result a correlation between the obtained carrier mobility and the strength of magnetic interaction. The greater mobility, the greater the intensity of the interaction.

Multiscale Analysis for Field-Effect Penetration through Two-Dimensional Materials

Gate-tunable two-dimensional (2D) materials-based quantum capacitors (QCs) and van der Waals heterostructures involve tuning transport or optoelectronic characteristics by the field effect. Recent studies have attributed the observed gate-tunable characteristics to the change of the Fermi level in the first 2D layer adjacent to the dielectrics, whereas the penetration of the field effect through the one-molecule-thick material is often ignored or oversimplified. Here, we present a multiscale theoretical approach that combines first-principles electronic structure calculations and the Poisson–Boltzmann equation methods to model penetration of the field effect through graphene in a metal–oxide–graphene–semiconductor (MOGS) QC, including quantifying the degree of “transparency” for graphene two-dimensional electron gas (2DEG) to an electric displacement field. We find that the space charge density in the semiconductor layer can be modulated by gating in a nonlinear manner, forming an accumulation or inversion layer at the semiconductor/graphene interface. The degree of transparency is determined by the combined effect of graphene quantum capacitance and the semiconductor capacitance, which allows us to predict the ranking for a variety of monolayer 2D materials according to their transparency to an electric displacement field as follows: graphene > silicene > germanene > WS2 > WTe2 > WSe2 > MoS2 > phosphorene > MoSe2 > MoTe2, when the majority carrier is electron. Our findings reveal a general picture of operation modes and design rules for the 2D-materials-based QCs.

Manifestation of Colossal Thermoelectric Power by Charge Ordered Small and Intermediate Bandwidth Manganites

Thermoelectric materials are revisited for various applications including power generation. The direct conversion of temperature differences into electric voltage and vice versa is known as thermoelectric effect. Possible applications of thermoelectric materials are in eco-friendly refrigeration, electric power generation from waste heat, infrared sensors, temperature controlled-seats and portable picnic coolers. Thermoelectric materials are also extensively researched upon as an alternative to compression based refrigeration. This utilizes the principle of Peltier cooling. The performance characteristic of a thermoelectric material, termed as figure of merit (ZT) is a function of several transport coefficients such as electrical conductivity (σ), thermal conductivity (κ) and Seebeck coefficient of the material (S). ZT is expressed asκσTZTS2=, where T is the temperature in degree absolute. A large value of Seebeck coefficient, high electrical conductivity and low thermal conductivity are necessary to realize a high performance thermoelectric material. The best known thermoelectric materials are phonon-glass electron – crystal (PGEC) system where the phonons are scattered within the unit cell by the rattling structure and electrons are scattered less as in crystals to obtain a high electrical conductivity. A survey of literature reveals that correlated semiconductors and Kondo insulators containing rare earth or transition metal ions are found to be potential thermoelectric materials. The structural magnetic and charge transport properties in manganese oxides having the general formula of RE1−xAExMnO3 (RE = rare earth, AE= Ca, Sr, Ba) are solely determined by the mixed valence (3+/4+) state of Mn ions. In strongly correlated electron systems, magnetism and charge transport properties are strongly correlated. Within the area of strongly correlated electron systems the study of manganese oxides, widely known as manganites exhibit unique magneto electric transport properties, is an active area of research.Strongly correlated systems like perovskite manganites, characterized by their narrow localized band and hoping conduction, were found to be good candidates for thermoelectric applications. Manganites represent a highly correlated electron system and exhibit a variety of phenomena such as charge, orbital and magnetic ordering, colossal magneto resistance and Jahn-Teller effect. The strong inter-dependence between the magnetic order parameters and the transport coefficients in manganites has generated much research interest in the thermoelectric properties of manganites. Here, large thermal motion or rattling of rare earth atoms with localized magnetic moments is believed to be responsible for low thermal conductivity of these compounds. The 4f levels in these compounds, lying near the Fermi energy, create large density of states at the Fermi level and hence they are likely to exhibit a fairly large value of Seebeck coefficient.

The Redox Potentials of n-type Colloidal Semiconductor Nanocrystals

Thesis (Ph.D.)--University of Washington, 2016-08

Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work.