Copper (Cu) electrodeposition on ruthenium (Ru) oxides was studied due to important implications in semiconductor industry. Ruthenium, proposed as the copper diffusion barrier/liner material, has higher oxygen affinity to form different oxides. Three different oxides (the native oxide, reversible oxide, and irreversible oxide) were studied. Native oxide can be formed on exposing Ru in atmosphere. The reversible and irreversible oxides can be formed by applying electrochemical potential. Investigation of Cu under potential deposition on these oxides indicates the similarity between native and reversible oxides by its nature of inhibiting Cu deposition. Irreversible oxide formed on Ru surface is rather conductive and interfacial binding between Cu and Ru is greatly enhanced. After deposition, bimetallic corrosion of Cu/Ru in different polyphenols was studied. Polyphenols are widely used as antioxidants in post chemical mechanical planarization (CMP). For this purpose, different trihydroxyl substituted benzenes were used as antioxidants. Ru, with its noble nature enhances bimetallic corrosion of Cu. Gallic acid (3,4,5 - trihydroxybenzoic acid) was chosen as model compound. A mechanism has been proposed and validity of the mechanism was checked with other antioxidants. Results show that understanding the chemical structure of antioxidants is necessary during its course of reaction with Cu.

Nanoenergetic composite materials have been synthesized by a sol-gel chemical process where the addition of a weak base molecule induces the gelation of a hydrated metal salt solution. A proposed proton scavenging mechanism, where a weak base molecule extracts a proton from the coordination sphere of the hydrated iron (III) complex in the gelation process to form iron (III) oxide/hydroxide, FeIIIxOyHz, has been confirmed for the weak base propylene oxide (PO), a 1,2 epoxide, as well as for the weak bases tetrahydrofuran (THF), a 1,4 epoxide, and pyridine, a heterocyclic nitrogen-containing compound. THF follows a similar mechanism as PO; the epoxide extracts a proton from the coordination sphere of the hydrated iron complex forming a protonated epoxide which then undergoes irreversible ring-opening after reaction with a nucleophile in solution. Pyridine also extracts a proton from the hydrated metal complex, however, the stable six-membered molecule has low associated ring strain and does not endure ring-opening. Fe2O3/Al energetic systems were synthesized from the epoxides PO, trimethylene oxide (TMO) and 3,3 dimethyl oxetane (DMO). Surface area analysis of the synthesized matrices shows a direct correlation between the surface area of the iron (III) oxide matrix and the quantified exothermic heat of reaction of the nano-scaled aluminum-containing energetic material due to the magnitude of the interfacial surface area contact between the iron (III) oxide matrix and the aluminum particles. The Fe2O3(PO)/Al systems possess the highest heat of reaction values due to the oxide interfacial surface area available for contact with the aluminum particles. Also, reactions containing nano-scale aluminum react differently than those containing micron-scale aluminum. RuO2/Al energetic systems behave differently dependent on the atmosphere the sample is heated. Heating the RuO2/Al samples in an inert atmosphere results in the complete reduction of the ruthenium oxide matrix to Ru(0) before reaction with the aluminum particles, resulting in the exothermic formation of RuxAly intermetallics, with the stoichiometry dependent on the initial Ru:Al concentration. However, heating the samples in an oxygen-rich atmosphere results in an exothermic reaction between RuO2 and Al.

No description available.

The search for novel quantum states is a fundamental theme in condensed matter physics. The almost boundless number of possible materials and complexity of the theory of electrons in solids make this both an experimentally and theoretically exciting and challenging research field. Particularly, the concept of quantum criticality resulted in a range of discoveries of novel quantum phases, which can become thermodynamically stable in the vicinity of a second order phase transition at zero temperature due to the existence of quantum critical fluctuations. One of the materials in which a novel quantum phase is believed to form close to a proposed quantum critical point is Sr₃Ru₂O₇. In this quasi-two-dimensional metal, the critical end point of a line of metamagnetic first order phase transitions can be suppressed towards zero temperature, theoretically leading to a quantum critical end point. Before reaching absolute zero, one experimentally observes the formation of an anomalous phase region, which has unusual ‘nematic-like’ transport properties. In this thesis magnetocaloric effect and specific heat measurements are used to systematically study the entropy of Sr₃Ru₂O₇ as a function of both magnetic field and temperature. It is shown that the boundaries of the anomalous phase region are consistent with true thermodynamic equilibrium phase transitions, separating the novel quantum phase from the surrounding ‘normal’ states. The anomalous phase is found to have a higher entropy than the low and high field states as well as a temperature dependence of the specific heat which deviates from standard Fermi liquid predictions. Furthermore, it is shown that the entropy in the surrounding ‘normal’ states increases significantly towards the metamagnetic region. In combination with data from other experiments it is concluded that these changes in entropy are most likely caused by many body effects related to the underlying quantum phase transition.

No description available.

Philosophiae Doctor - PhD

No description available.

People suffering from certain types of arrhythmia may benefit from the implantation of a cardiac pacemaker. Pacemakers artificially stimulate the heart by applying short electrical pulses to the cardiac tissue to restore and maintain a steady heart rhythm. By adjusting the pulse delivery rate the heart is stimulated to beat at desired pace. The stimulation pulses are transferred from the pacemaker to the heart via an electrode, which is implanted into the cardiac tissue. Additionally, the electrode must also sense the cardiac response and transfer those signals back to the electronics in the pacemaker for processing. The communication between the electrode and the tissue takes place on the electrode/electrolyte (tissue) interface. This interface serves as the contact point where the electronic current in the electrode is converted to ionic currents capable to operate in the body. The stimulation/sensing signals are transferred across the interface via three electrochemical mechanisms: i) non-faradaic charging/discharging of the electrochemical double layer, ii) reversible and iii) irreversible faradaic reactions. It is necessary to study the contribution of each mechanism to the total charge transferred to evaluate the pacing/sensing performance of the pacemaker electrode. In this thesis, the electrochemical properties and performance of stimulation/sensing electrodes for pacemaker applications have been investigated by electrochemical impedance spectroscopy, cyclic voltammetry and transient electrochemical techniques. All measurements were performed in synthetic body fluid with buffer capacity. Complementary surface analysis was performed with scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The results reveal different interfacial behaviour and stability for electrode materials such as Pt, TiN, porous carbon, conducting oxides (RuO2 and IrO2 and mixed oxides) and porous Nb2O5 oxide. The influence of the charge/discharge rate on the electrode characteristics also has been evaluated. Although the rough and porous electrodes provide a high interfacial capacitance, the maximum capacitance cannot be fully employed at high charge/discharge rates because only a small part of the effective surface area is accessible. The benefit of pseudo-capacitive material properties on charge delivery was observed. However, these materials suffer similar limitations at high charge/discharge rate and, hence, are only utilising the surface bound pseudo-capacitive sites. Porous Nb2O5 electrodes were investigated to study the performance of capacitor electrodes. These electrodes predominantly deliver the charge via reversible non-faradaic mechanisms and hence do not produce irreversible by-products. They can deliver very high potential pulses while maintaining high impedance and, thus, charge lost by faradaic currents are kept low. By producing Nb oxide by plasma electrolysis oxidation a porous surface structure is obtained which has the potential to provide a biocompatible interface for cell adherence and growth. This thesis covers a multidisciplinary area. In an attempt to connect diverse fields, such as electrophysiology, materials science and electrochemistry, the first chapters have been attributed to explaining fundamental aspects of the respective fields. This thesis also reviews the current opinion of pacing and sensing theory, with special focus on some areas where detailed explanation is needed for the fundamental nature of electrostimulation/sensing. / QC 20101014

The Antimatter Experiment: Gravity, Interferometry, Spectroscopy (AEGIS) at the European Organization for Nuclear Research (CERN) is an experiment investigating the influence of earth’s gravitational force upon antimatter. To perform precise measurements the antimatter needs to be cooled to a temperature of 100 mK. This will be done in a Penning trap, formed by several electrodes, which are charged with several kV and have to be individually electrically insulated. The trap is thermally linked to a mixing chamber of a 3He-4He dilution refrigerator. Two link designs are examined, the Rod design and the Sandwich design. The Rod design electrically connects a single electrode with a heat exchanger, immersed in the helium of the mixing chamber, by a copper pin. An alumina ring and the helium electrically insulate the Rod design. The Sandwich uses an electrically insulating sapphire plate sandwiched between the electrode and the mixing chamber. Indium layers on the sapphire plate are applied to improve the thermal contact. Four differently prepared test Sandwiches are investigated. They differ in the sapphire surface roughness and in the application method of the indium layers. Measurements with static and sinusoidal heat loads are performed to uncover the behavior of the thermal boundary resistances. The thermal total resistance of the best Sandwich shows a temperature dependency of T-2,64 and is significantly lower, with roughly 30 cm2K4/W at 50 mK, than experimental data found in the literature. The estimated thermal boundary resistance between indium and sapphire agrees very well with the value of the acoustic mismatch theory at low temperatures. In both designs, homemade heat exchangers are integrated to transfer the heat to the cold helium. These heat exchangers are based on sintered structures to increase the heat transferring surface and to overcome the significant influence of the thermal resistance (Kapitza resistance). The heat exchangers are optimized concerning the adherence of the sinter to the substrate and its sinter height, e.g. its thermal penetration length. Ruthenium oxide metallic resistors (RuO2) are used as temperature sensors for the investigations. They consist of various materials, which affect the reproducibility. The sensor conditioning and the resulting good reproducibility is discussed as well.

The Antimatter Experiment: Gravity, Interferometry, Spectroscopy (AEGIS) at the European Organization for Nuclear Research (CERN) is an experiment investigating the influence of earth’s gravitational force upon antimatter. To perform precise measurements the antimatter needs to be cooled to a temperature of 100 mK. This will be done in a Penning trap, formed by several electrodes, which are charged with several kV and have to be individually electrically insulated. The trap is thermally linked to a mixing chamber of a 3He-4He dilution refrigerator. Two link designs are examined, the Rod design and the Sandwich design. The Rod design electrically connects a single electrode with a heat exchanger, immersed in the helium of the mixing chamber, by a copper pin. An alumina ring and the helium electrically insulate the Rod design. The Sandwich uses an electrically insulating sapphire plate sandwiched between the electrode and the mixing chamber. Indium layers on the sapphire plate are applied to improve the thermal contact. Four differently prepared test Sandwiches are investigated. They differ in the sapphire surface roughness and in the application method of the indium layers. Measurements with static and sinusoidal heat loads are performed to uncover the behavior of the thermal boundary resistances. The thermal total resistance of the best Sandwich shows a temperature dependency of T-2,64 and is significantly lower, with roughly 30 cm2K4/W at 50 mK, than experimental data found in the literature. The estimated thermal boundary resistance between indium and sapphire agrees very well with the value of the acoustic mismatch theory at low temperatures. In both designs, homemade heat exchangers are integrated to transfer the heat to the cold helium. These heat exchangers are based on sintered structures to increase the heat transferring surface and to overcome the significant influence of the thermal resistance (Kapitza resistance). The heat exchangers are optimized concerning the adherence of the sinter to the substrate and its sinter height, e.g. its thermal penetration length. Ruthenium oxide metallic resistors (RuO2) are used as temperature sensors for the investigations. They consist of various materials, which affect the reproducibility. The sensor conditioning and the resulting good reproducibility is discussed as well.