Die vorliegende Arbeit befasst sich mit Elektronenenergieverlustspektroskopie an unterdotierten Kupratsupraleitern und Übergangsmetalldichalcogeniden. Nach einem kurzen Abriss über die der experimentellen Methode zugrundeliegenden theoretischen Tatsachen folgen zwei experimentelle Kapitel. Für das prototypische Kupratsystem Ca2-xNaxCuO2Cl2 wird für verschiedene Dotierungskonzentrationen zunächst die Entwicklung der Ladungstransferanregungen untersucht. Man findet eine substanzielle Umverteilung des spektralen Gewichtes, verbunden mit einem starken Einbruch der Dispersion dieser Anregungen. Beides wird im Rahmen der Wechselwirkung mit Spinfreiheitsgraden innerhalb der Kupfer-Sauerstoff-Ebene diskutiert. Anschliessend erfolgt die Diskussion einer ausschließlich für zehnprozentige Dotierung auftretenden Symmetriebrechung der optischen Antwortfunktion, für die verschiedene mögliche Szenarien vorgeschlagen werden. Im Kapitel über die Dichalcogenide liegt der Fokus auf dem Verhalten des Ladungsträgerplasmons, das für alle Substanzen dieser Gruppe mit Ladungsordnung eine negative Dispersion aufweist. Dieses Verhalten läßt sich durch in-situ Interkalation zusätzlicher Ladungstraeger umkehren, so dass man eine dotierungsabhängige Plasmonendispersion erhält. Es werden verschiedene Szenarien für dieses Verhalten diskutiert. / The present thesis describes electron energy-loss spectroscopy on underdoped cuprate superconductors and transition-metal dichalcogenides. After a brief introduction into the experimental method there are two experimental chapters. For the prototype cuprate system Ca2-xNaxCuO2Cl2 the behavior of the charge-transfer excitations is investigated as a function of doping. The observed substantial redistribution of spectral weight and the accompanying breakdown of their dispersion is discussed in terms of a coupling to the spin degrees of freedom within the copper-oxygen plane. For x=0.1 there is a pronounced symmetry breaking in the optical response function which is discussed in terms of different possible scenarios. The chapter on the dichalcogenides focuses on the properties of the charge-carrier plasmon which shows a negative dispersion for all representatives of this family exhibiting a charge-density wave instability. This behavior can be influenced by in-situ intercalation of additional charges, the result being a doping dependent plasmon dispersion. Several approaches to reconcile these findings are considered.

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

In this thesis, we present a detailed investigation of the electronic properties of particular transition-metal dichalcogenides. Applying electron-energy loss spectroscopy, the connection between the negative plasmon dispersion of tantalum diselenide and the occurrence of a charge-density wave state (CDW) in this compound as well as related materials is observed. Our studies include doping experiments with alkali metal addition altering the charge density of the compounds. This is known to suppress the CDW. We show that it further changes the plasmon dispersion from negative to positive slope. To estimate the doping rate of the investigated tantalum diselenide samples, a density functional theory approach is introduced, giving reliable results for a quantitative analysis of our findings. We refer to a theoretical model to describe the connection of the charge ordering and the plasmon dynamics. Investigations of the non-CDW compound niobium disulfide give further insights into the proposed interaction. Experimental results are further evaluated by a Kramers-Kronig-analysis. A structural analysis, by means of elastic electron scattering, shows the CDW to be suppressed upon doping, giving space for an emerging superstructure related to the introduced K atoms. / In der vorliegenden Arbeit wird eine detaillierte Untersuchung der elektronischen Eigenschaften von ausgewählten Übergangsmetall-Dichalcogeniden präsentiert. Unter Anwendung von Elektronenenergieverlust-Spektroskopie wird die Verbindung der negativen Plasmomendispersion in Tantaldiselenid zum Auftreten eines Ladungsdichtewelle-Zustands (CDW) in diesem und in verwandten Materialien untersucht. Die Untersuchungen schließen Dotierungsexperimente mit dem Zusatz von Alkalimetallen ein, die die Ladungsdichte der Proben beeinflussen. Einerseits unterdrückt dies die CDW. Es wird außerdem gezeigt, dass sich der Anstieg der Plasmonendispersion von negativ zu positiv ändert. Ein Dichtefunktional-Theorie-Zugang zur Abschätzung der Dotierungsraten der untersuchten Tantaldiselenid-Proben wird genutzt, um verlässliche Ergebnisse für die quantitative Analyse unserer Messungen zu erhalten. Ein theoretisches Modell wird einbezogen, welches die Verbindung der Ladungsordung zur kollektiven Anregung der Ladungsdichte beschreibt, Untersuchungen der nicht-CDW Substanz Niobdisulfid geben weitere Einblicke in die Verbindung der beiden Phänomene. Die experimentellen Resultate werden weiterhin mit einer Kramers-Kronig-Analyse ausgewertet. Strukturelle Untersuchungen mit elastischer Elektronenstreuung zeigen, wie die CDW unterdrückt wird und einer auftauchenden Überstruktur, verursacht von den interkalierten K-Atomen, Raum gibt.

Formation of charge density waves (CDW) is a symmetry breaking phenomenon found in electronic systems, which is particularly common in quasi-one-dimensional conductors. It is widely observed from highly anisotropic materials to isotropic ones like the superconducting pnictides. The CDW is seen as a sinusoidal deformation of coupled electronic density and lattice modulation; it can be also viewed as a crystal of singlet electronic pairs. In the CDW state, the elementary units can be readjusted by absorbing or rejecting pairs of electrons. Such a process should go via topologically nontrivial configurations: solitons and dislocations - the CDW vortices. An experimental access to these inhomogeneous CDW states came from studies of nano-fabricated mesa-junctions, from the STM and from the X-ray micro-diffraction. Following these requests, we have performed a program of modeling stationary states and of their transient dynamic for the CDW in restricted geometries under applied voltage or at passing normal currents. The model takes into account multiple fields in mutual nonlinear interactions: the two components of the CDW complex order parameter, and distributions of the electric field, the density and the current of normal carriers. We were using the Ginzburg-Landau type approach and also we have derived its extension based on the property of the chiral invariance. We observed the incremental creation of static dislocations within the junctions. The transient dynamics is very rich showing creation, annihilation and sweeping of multiple vortices. The dislocations cores concentrate the voltage drops thus providing self-tuned microscopic junctions where the tunneling creation of electron-hole pairs can take place. The results obtained from this model agree with experiment observations. The methods can be extended to other types of charge organization known under the general name of the Electronic Crystal. It takes forms of Wigner crystals at hetero-junctions and in nano-wires, CDWs in chain compounds, spin density waves in organic conductors, and stripes in doped oxides. The studied reconstruction in junctions of the CDW may be relevant also to modern efforts of the field-effect transformations in strongly correlated materials with a spontaneous symmetry breaking.

It has long been observed that salts affect proteins in a variety of ways, yet comprehensive explanations for different salt effects are still lacking. In the work presented here, the effect of salts on proteins has been investigated through three different effects: the hydrophobic effect; their conformational stability; the hydrogen bonding network of water in a protein’s hydration shell. UV-vis absorbance and fluorescence spectroscopy were used to monitor changes in two model systems, the phenol-acetate contact pair and the model enzyme ribonuclease t1. It was shown that salts affect the hydrophobicity of the contact pair according to their charge density, induced image charges play an important role in the observed salt-induced increase of ribonuclease t1 stability, and that salts affect ribonuclease t1 activity through modulation of the hydrogen bonds of water in the enzyme’s hydration shell. This work contributes a greater understanding of the effect of salts on proteins.

It has long been observed that salts affect proteins in a variety of ways, yet comprehensive explanations for different salt effects are still lacking. In the work presented here, the effect of salts on proteins has been investigated through three different effects: the hydrophobic effect; their conformational stability; the hydrogen bonding network of water in a protein’s hydration shell. UV-vis absorbance and fluorescence spectroscopy were used to monitor changes in two model systems, the phenol-acetate contact pair and the model enzyme ribonuclease t1. It was shown that salts affect the hydrophobicity of the contact pair according to their charge density, induced image charges play an important role in the observed salt-induced increase of ribonuclease t1 stability, and that salts affect ribonuclease t1 activity through modulation of the hydrogen bonds of water in the enzyme’s hydration shell. This work contributes a greater understanding of the effect of salts on proteins.

Made available in DSpace on 2014-12-17T14:07:19Z (GMT). No. of bitstreams: 1 DianaCSL.pdf: 800391 bytes, checksum: c85f3fef7e600f91edb93d3096219c80 (MD5) Previous issue date: 2005-11-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The addition of active silica potentially improves the quality of concrete due to its high reactivity and pore refinement effect. The reactivity of silica is likely related to its charge density. Variations in surface charge alter the reactivity of the material consequently affecting the properties of concrete. The present study aimed at investigating variations in the charge density of silica as a function of acid treatments using nitric or phosphoric acid and different pH values (2.0, 4.0 and 6.0). Effects on concrete properties including slump, mechanical strength, permeability and chloride corrosion were evaluated. To that end, a statistical analysis was carried out and empirical models that correlate studied parameters (pH, acid and cement) with concrete properties were established. The quality of the models was tested by variance analysis. The results revealed that the addition of silica was efficiency in improving the properties of concrete, especially the electrochemical parameters. The addition of silica treated using nitric acid at pH = 4.0 displayed the best cement performance including highest strength, reduced permeability and lowest corrosion current / A adi??o da s?lica ativa ao concreto melhora a qualidade deste material, amplamente utilizado na Constru??o Civil, devido ? a??o dos efeitos: alta reatividade e refinamento dos poros. Acreditando-se que a reatividade da s?lica est? relacionada ? sua densidade de carga, uma varia??o da carga superficial modifica a reatividade do material, e consequentemente as propriedades do concreto. Assim, este trabalho objetiva estudar o efeito da varia??o da densidade de carga superficial da s?lica tratada com solu??es de ?cidos n?trico e fosf?rico a diferentes pHs: 2,0; 4,0 e 6,0 em propriedades do concreto: abatimento, resist?ncia ? compress?o, permeabilidade e par?metros indicativos do processo de corros?o por cloreto. Para tanto, realizou-se um planejamento experimental com a finalidade de obter modelos emp?ricos que relacionam as propriedades e par?metros avaliados com as vari?veis em estudo: pH, tipo de ?cido e tipo de cimento, bem como a an?lise de vari?ncia indicativa da qualidade do modelo proposto em rela??o ?s observa??es experimentais. Os resultados comprovaram a efic?cia da adi??o de s?lica ativa na mistura de concreto ?s propriedades estudadas. Indicam que uma varia??o na densidade de carga superficial da s?lica usada na confec??o de corpos de prova de concreto modifica as propriedades e par?metros eletroqu?micos estudados e que, o concreto com uso de s?lica tratada com solu??o de ?cido n?trico de pH 4,0, apresentou melhor qualidade: maior resist?ncia ? compress?o, menor permeabilidade e menor corrente de corros?o, quando tomados em rela??o aos demais

Submitted by EVERLIN CAROLINA FERREIRA DA SILVA null (everlinferreira@hotmail.com) on 2016-04-19T16:13:05Z No. of bitstreams: 1 DissertaçãoFinal.pdf: 3642722 bytes, checksum: f19af99a16e56b2846a689e39c66c05b (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-04-20T19:11:13Z (GMT) No. of bitstreams: 1 silva_ecf_me_rcla.pdf: 3642722 bytes, checksum: f19af99a16e56b2846a689e39c66c05b (MD5) / Made available in DSpace on 2016-04-20T19:11:13Z (GMT). No. of bitstreams: 1 silva_ecf_me_rcla.pdf: 3642722 bytes, checksum: f19af99a16e56b2846a689e39c66c05b (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A técnica de espectroscopia de impedância foi aplicada para caracterizar um monocristal da ludwigita homometálica Fe3O2BO3, em que uma transição de ordenamento de carga (CO) ocorre em temperatura ambiente (~ 300 K) conforme reportada na literatura. Utilizando diferentes valores de amplitude do sinal AC aplicado, pudemos pelo estudo do comportamento da condutividade AC identificar nessas medidas o fenômeno de soltura de ondas de densidade de carga (CDW) e usamos a teoria de Bardeen, na faixa de temperatura em que foi possível aplica-la, para obter a razão entre a massa do condensado MF e a massa m do elétron, da ordem de 109 - 107. As características deste material foram comparadas a uma amostra de um sistema sem ordenamento de carga reportada, uma pastilha prensada de α-MnO2 dopado com cobre. Para ambos os materiais informação sobre o comportamento da constante dielétrica também foi obtido. / The impedance spectroscopy technique was applied to the characterization of a single crystal of the homometallic ludwigite Fe3O2BO3, in which a charge ordering transition (CO) occurs around room temperature (~ 300K), as reported in the literature. By using different values of the AC amplitude signal we could study the AC conductivity behavior and identify the depinning of the charge-density wave phenomenon (CDW). Applying the Bardeen theory, in a proper temperature range, to obtain the rate of the mass of the condensate MF in relation to that of the electron m, we found a ratio the order of 109 - 107 . The characteristics of this material were compared with a system without reported charge ordering transition, Cu doped α-MnO2 pressed pellets. For both materials, information about the behavior of the dielectric constant was also obtained.

The study of cuprate high-temperature superconductors has undergone a recent resurgence due to the discovery of charge order in several families of cuprate materials. While its existence is now well established, little is known about its microscopic origins or its relationship to high-temperature superconductivity and the pseudogap. The aim of the research presented in this thesis is to address these questions. In this thesis I will report on the use of spectroscopic-imaging scanning tunnelling microscopy (SI-STM) to visualise the short-ranged charge density wave (CDW) in Bi₂Sr₂CaCu₂O₈₊ₓ and NaxCa₂₋ₓCuO₂Cl₂. Building on previous measurements of the intra unit-cell electronic structure of cuprates, I introduce sub-lattice segregated SISTM to individually address the atomic sub-lattices in the CuO₂ plane with spatial phase sensitivity. Using this technique I establish that the CDW in Bi₂Sr₂CaCu₂O₈+x and NaxCa₂₋ₓCuO₂Cl₂ has a previously unobserved d-symmetry form factor, where a breaking of rotational symmetry within the unit cell is modulated periodically in space. Towards identifying a mechanism of CDW formation, I establish that the amplitude of CDW modulations in the electronic structure are maximal at the pseudogap energy-scale and that these modulations exhibit a spatial phase difference of π between filled and empty states. Together with the doping evolution of the CDW wave-vector this highlights the role of the low-energy electronic structure of the pseudogap regime in CDW formation. To elucidate the relationship between the CDW and the superconducting condensate I will introduce nanometer resolution scanned Josephson tunnelling microscopy (SJTM). In this approach the Cooper pair (Josephson) tunnelling current between a Bi₂Sr₂CaCu₂O₈₊ₓ sample and a scan-able Bi₂Sr₂CaCu₂O₈₊ₓ nano-flake STM tip is used to directly visualise the superconducting condensate. I will report the observation of a periodic modulation in the Cooper pair condensate at the same wave-vector as the CDW, the first direct detection of a periodically modulating condensate in any superconductor.

Cette thèse présente une étude expérimentale de l'interaction entre la supraconductivité et une onde de densité de charge (ODC). Dans la théorie standard, la température critique d’un matériau supraconducteur est favorisée principalement par deux paramètres : une grande densité d’états au niveau de Fermi (nF), et un fort couplage électron-phonon. Cependant, un fort couplage électron-phonon favorise aussi l’apparition d’une ODC, ce qui réduit nF et rivalise ainsi avec la supraconductivité.Notre démarche a consisté à étudier deux composés où supraconductivité et ODC coexistent, et dans lesquels on peut faire disparaître l’ODC grâce à un paramètre externe : pression ou substitution. Le premier composé, 2H-NbSe2, présente une ODC en dessous de 33 K à pression ambiante. Celle-ci coexiste avec la supraconductivité en dessous de 7 K. Sous pression, l’ODC disparaît au-dessus de 4.6 GPa, sans que la température critique varie notablement. L’ODC disparaît aussi en remplaçant le sélénium par du soufre : 2H-NbS2 est ainsi un supraconducteur sans ODC (Tc = 6 K), et peut donc servir de composé témoin pour une étude comparative. Dans le second composé, Lu5Ir4Si10, une ODC est présente en dessous de 77 K à pression ambiante. Celle-ci disparaît sous pression au-dessus de 2 GPa, tandis que la température critique saute simultanément de 4 à 9 K. Pour étudier ces composés, j’ai utilisé trois techniques expérimentales : la mesure de la dispersion des phonons à basse température (300-2 K) et sous pression (0-16 GPa) par diffusion inélastique des rayons X, la mesure de la dépendance en température de la longueur de pénétration magnétique grâce à un oscillateur à diode tunnel et la mesure des champs critiques via des microsondes Hall.Dans la première partie, je présente la dépendance en température de la dispersion des phonons dans 2H-NbS2. Nous observons la présence d’un phonon mou dont l’énergie reste toujours positive, même extrapolée à température nulle. Ce composé est ainsi à la limite d'une instabilité ODC. De plus, nous montrons qu’il est relativement unique, car seuls les effets anharmoniques empêchent l’amollissement complet des phonons. Je présente ensuite la dépendance en température et en pression de la dispersion des phonons dans 2H-NbSe2. Ces expériences montrent qu’un mode de phonon mou persiste jusqu’à 16 GPa, même quand l'état à température nulle n'est pas l’ODC. La dépendance en température de ce phonon mou est alors similaire à celle de 2H-NbS2. Dans les deux composés, ces phonons mous semblent liés à la présence d'un couplage électron-phonon à la fois fort et anisotrope. Nous suggérons qu’il s’agit d’un élément essentiel pour expliquer leurs propriétés supraconductrices.Dans la seconde partie, je mesure l'anisotropie et la dépendance en température de la longueur de pénétration magnétique dans l’état supraconducteur de 2H-NbS2 et Lu5Ir4Si10. La dépendance en température de la densité superfluide dans 2H-NbS2 confirme la présence d'un gap supraconducteur réduit dont l'amplitude est très proche de celle mesurée dans 2H-NbSe2. Les phonons mous et le gap réduit étant présents dans 2H-NbS2 et 2H-NbSe2, nous prouvons expérimentalement qu'il faut raisonner en termes de renforcement de la supraconductivité par les phonons mous plutôt qu'en termes d’interaction avec l'état fondamental (ODC ou métal). Nous proposons que ce renforcement soit lié à l'anisotropie du couplage électron-phonon.En revanche, cet effet n’est pas général aux composés où supraconductivité et ODC coexistent. Les propriétés supraconductrices de Lu5Ir4Si10 sont en effet bien décrites par le modèle BCS couplage faible. Ceci est peut être lié aux caractéristiques de l’ODC : la présence d’une hystérésis montre que la transition ODC est du premier ordre. D’autre part, les mesures de diffraction X sous pression et à basse température révèlent que cette ODC est multiple : en plus de la périodicité 1/7, nous observons une seconde périodicité de 1/20. / This thesis presents an experimental study of the interaction between superconductivity and a charge density wave (CDW). In the standard theory, the critical temperature of a superconductor is principally enhanced by two parameters: a large density of states at the Fermi level (nF) and a strong electron-phonon coupling. However, a strong electron-phonon coupling also favors the appearance of a CDW, which reduces nF and therefore competes with superconductivity.Our strategy was to study two compounds in which superconductivity and CDW coexist, and in which the CDW can be suppressed through an external parameter: pressure or substitution. The first compound is 2H-NbSe2, it presents a CDW below 33 K at ambient pressure. This CDW coexists with superconductivity below 7 K. Under pressure, the CDW disappears above 4.6 GPa, meanwhile the critical temperature slowly changes. The CDW also disappears when replacing selenium by sulfur: 2H-NbS2 is a superconductor without CDW (Tc=6 K), it can therefore serve as a “test compound” for a comparative study. The second compound is Lu5Ir4Si10, it presents a CDW below 77 K at ambient pressure. Under pressure, this CDW disappears above 2 GPa, meanwhile the critical temperature abruptly jumps from 4 to 9 K.For this study, I used three experimental techniques: inelastic x-ray scattering at low temperature (300-2 K) and under pressure (0-16 GPa) to measure the dispersion of phonons, a tunnel diode oscillator to measure the temperature dependence of the magnetic penetration depth, and Hall microprobes to measure the first and second critical fields. In the first part, I present the temperature dependence of the phonon dispersion in 2H-NbS2. We observe a soft phonon that always remains at positive energies, even extrapolated to zero temperature. Thus, this compound is on the verge of CDW instability. It is also relatively unique, since we show anharmonicity is the only effect that prevents the complete softening of the phonons.Then I present the temperature and pressure dependence of the phonon dispersion in 2H-NbSe2. These experiments show that a soft phonon persists up to 16 GPa, even if the ground state is not a CDW. The temperature dependence of this soft phonon is then similar to that of 2H-NbS2. In both compounds, these soft modes seem to be related to the strength and anisotropy of the electron-phonon coupling. We suggest this is a fundamental element to explain their superconducting properties.In the second part, I measure the anisotropy and temperature dependence of the magnetic penetration depth in the superconducting state of 2H-NbS2 and Lu5Ir4Si10. The temperature dependence of the superfluid density in 2H-NbS2 confirms the presence of a reduced superconducting gap. Its amplitude is very similar to the one measured in 2H-NbSe2. The soft modes and the reduced gap being present in both 2H-NbSe2 and 2H-NbS2, we prove experimentally that the enhancement of superconductivity is related to the soft modes rather than to the nature of the ground state (CDW or metal). We suggest this enhancement is due the anisotropy of the electron-phonon coupling.However, this effect is not general to all compounds where superconductivity and CDW coexist. The superconducting properties of Lu5Ir4Si10 are indeed well fitted by the BCS model in the weak coupling limit. This may be related to the characteristics of the CDW: the presence of hysteresis shows that the CDW transition is first order. In addition, under pressure and at low temperature, x-ray diffraction measurements indicate that the CDW is multiple: aside from the periodicity of 1/7, we observe a second periodicity of 1/20.