As a very promising material of copper diffusion barrier for next generation microelectronics, Ru has already obtained a considerable attention recently. In this dissertation, we investigated ruthenium and ruthenium oxide electrochemical properties and the application as a copper diffusion barrier. Cu under potential deposition (UPD) on the RuOx formed electrochemically was first observed. Strong binding interaction, manifesting by the observed Cu UPD process, exists between Cu and Ru as well as its conductive ruthenium oxide. Since UPD can be conformally formed on the electrode surface, which enable Ru and RuOx has a potential application in the next generation anode. The [Cl-] and pH dependent experiment were conducted, both of them will affect UPD Cu on Ru oxide. We also found the Cu deposition is thermodynamically favored on RuOx formed electrochemically. We have studied the Ru thin film (5nm) as a copper diffusion barrier. It can successfully block Cu diffusion annealed at 300 oC for 10min under vacuum, and fail at 450 oC. We think the silicidation process at the interface between Ru and Si. PVD Cu/Ru/Si and ECP Cu/Ru/Si were compared each other during copper diffusion study. It was observed that ECP Cu is easy to diffuse through Ru barrier. The function of RuOx in diffusion study on Cu/Ru/Si stack was discussed. In pH 5 Cu2+ solution, Ru and Pt electrochemical behavior were investigated. A sharp difference was observed compared to low pH value. The mechanism in pH 5 Cu2+ solution was interpreted. An interesting compound (posnjakite) was obtained during the electrochemical process. An appropriate formation mechanism was proposed. Also Cu2O was formed in the process. We found oxygen reduction reaction is a key factor to cause this phenomenon.

The integration of copper (Cu) and dielectric materials has been outlined in the International Technology Roadmap for Semiconductors (ITRS) as a critical goal for future microelectronic devices. A necessity toward achieving this goal is the development of diffusion barriers that resolve the Cu and dielectric incompatibility. The focus of this research examines the potential use of tungsten nitride as a diffusion barrier by characterizing the interfacial properties with Cu and evaluating its process capability for industrial use. Tungsten nitride (β-W2N) development has been carried out using a plasma enhanced chemical vapor deposition (PECVD) technique that utilizes tungsten hexafluoride (WF6), nitrogen (N2), hydrogen (H2), and argon (Ar). Two design of experiments (DOE) were performed to optimize the process with respect to film stoichiometry, resistivity and uniformity across a 200 mm diameter Si wafer. Auger depth profiling showed a 2:1 W:N ratio. X-ray diffraction (XRD) showed a broad peak centered on the β-W2N phase. Film resistivity was 270 mohm-cm and film uniformity < 3 %. The step coverage (film thickness variance) across a structured etched dielectric (SiO2, 0.35 mm, 3:1 aspect ratio) was > 44 %. Secondary ion mass spectroscopy (SIMS) measurements showed good barrier performance for W2N between Cu and SiO2 with no intermixing of the Cu and silicon when annealed to 390o C for 3 hours. Cu nucleation behavior and thermal stability on clean and nitrided tungsten foil (WxN = δ-WN and β-W2N phases) have been characterized by Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) under controlled ultra high vacuum (UHV) conditions. At room temperature, the Auger intensity ratio vs. time plots demonstrates layer by layer Cu growth for the clean tungsten (W) surface and three-dimensional nucleation for the nitride overlayer. Auger intensity ratio vs. temperature measurements for the Cu/W system indicates a stable interface up to 1000 K. For the Cu /WxN/W system, initial Cu diffusion into the nitride overlayer is observed at 550 K.

Cadmium telluride (CdTe) is a leading thin film photovoltaic (PV) material due to its near ideal band gap of 1.45 eV, its high optical absorption coefficient and availability of various device fabrication methods. Superstrate CdTe solar cells fabricated on glass have to-date exhibited efficiencies of 16.5%. Work on substrate devices has been limited due to difficulties associated with the formation of an ohmic back contact with CdTe. The most promising approach used to-date is based on the use of an interlayer between the CdTe and a metal electrode, an approach that is believed to yield a pseudo-ohmic contact. This research investigates the use of ZnTe and Sb2Te3 as the interlayer, in the development of efficient back contacts. Excellent adhesion and minimum stress are also required of a CdTe thin film solar cell device on a flexible stainless steel (SS) foil substrate. Foil substrate curvature, flaking, delamination and adhesion as a result of compressive strain due to the coefficient of thermal expansion (CTE) mismatch between the flexible SS foil substrate and the solar cell films have been studied. A potential problem with the use of a SS foil as the substrate is the diffusion of iron (Fe), chromium (Cr) and other elemental impurities into the layers of the solar cell device structure during high temperature processing. A diffusion barrier limiting the out diffusion of these substrate elements is being investigated in this study. Silicon nitride (Si3N4) films deposited on SS foils are being investigated as the barrier layer, to reduce or inhibit the diffusion of substrate impurities into the solar cell. Thin film CdTe solar cells have been fabricated and characterized by AFM, XRD, SEM, ASTM D3359-08 tape test, current-voltage (I-V) and spectral measurements. My individual contributions to this work include the Molybdenum (Mo) development, the adhesion studies, the silicon nitride (Si3N4) barrier studies, and EDS and SEM lines measurements and analysis of substrate out-diffused impurities. The rest of my colleagues focused on the development of CdTe, CdS, ZnTe, the CdCl2 heat treatment, and other back contact interlayer materials.

The first part of this dissertation highlights the contents of the electrochemical characterization of Cu and its electroplating on Ru-based substrates. The growth of Ru native oxide does diminish the efficiency of Cu plating on Ru surface. However, the electrochemical formed irreversible Ru hydrate dioxide (RuOxHy) shows better coverage of Cu UPD. The conductive Ru oxides are directly plateable liner materials as potential diffusion barriers for the IC fabrication. The part II of this dissertation demonstrates the development of a new rapid corrosion screening methodology for effective characterization Cu bimetallic corrosion in CMP and post-CMP environments. The corrosion inhibitors and antioxidants were studied in this dissertation. In part III, a new SEC methodology was developed to study the ORR catalysts. This novel SEC cell can offer cheap, rapid optical screening results, which helps the efficient development of a better ORR catalyst. Also, the SEC method is capable for identifying the poisoning of electrocatalysts. Our data show that the RuOxHy processes several outstanding properties of ORR such as high tolerance of sulfation, high kinetic current limitation and low percentage of hydrogen peroxide.

Magnesium (Mg) is a light-weight metal that has extraordinary physical and chemical properties for many potential applications in automobile, military, and electronics. Aluminum alloys, because of its light-weight, high strength and corrosion resistance have a wide range of commercial applications. Given these two, sometime competing, alloy systems, there are now many applications where the metallurgical compatibility of Mg- and Al-alloys are required for engineering applications. One such case is the development of diffusion barrier for U-Mo metallic fuel in Al-alloy cladding, where Mg, with its complete immiscibility with U and Mo is being considered as the diffusion barrier. While negligible diffusional interaction between Mg and U-Mo alloys have been reported, diffusional interaction between the Mg and Al-alloy cladding has not been investigated. In this study, solid-to-solid diffusion couples were assembled using discs of pure Mg (99.999 %) and AA6061 Al-alloy. After preparation, Mg was diffusion bonded to AA6061 in sealed quartz capsule at 300°, 350°, and 400°C for 720, 360, and 240 hours, respectively. Scanning electron microscopy was used to inspect the interdiffusion zone, while phase identification was performed using X-ray energy dispersive spectroscopy. One specific phase that exists in the binary Mg-Al system, labeled “ε” was observed and characterized by transmission electron microscopy. From the preceding data, the growth rates as well as interdiffusion coefficients of the intermetallic phases were extracted and compared to previous investigations using pure Mg and Al.

A reliable and robust diffusion barrier, commonly known as under bump metallisation (UBM), is indispensable in solder interconnects in order to retard the interfacial reaction rate, hence the growth of intermetallic compounds (IMCs). However, electroless Ni-P coatings are not adequate to inhibit interfacial reactions effectively since the formation of columnar structure and voids in the crystalline Ni3P layer in hybrid automotive devices (operating temperature above 300ºC) can significantly deteriorate the mechanical integrity of solder joints. In this thesis, electroless Ni-W-P coatings, as an effective UBM capable to serving under high temperature (up to 450ºC), are developed, characterised and subsequently applied onto the high temperature lead-free solder interconnects.

Because of their good mechanical resistance at high temperature, Ni-based superalloys are used for aero-engine and land-based turbines but undergo "dry" oxidation between 900 and 1500°C. These materials are thus coated with nickel-aluminide coatings (BC). An additional thermal barrier coating (TBC) is generally applied in the hottest sections of the turbines (T>1050°C) to lower the impact of the temperature on the substrate. In the framework of the European research programme "PARTICOAT", this PhD work was focused on the growth mechanisms of a full protective coating system (BC+TBC) in a single step process, using a water-based slurry containing a dispersion of Al micro-particles to satisfy the European environmental directives. The rheological and physico-chemical characterizations showed the slurry stability up to seven days. After depositing the latter by air spraying, a tailored thermal treatment resulted in a nickel-aluminide coating (β-NiAl) similar to the conventional industrial ones but through an intermediate Al liquid phase stage. Simultaneously, the oxidation of the Al micro-particles brought aboutthe formation of a top alumina "foam" (PARTICOAT concept). After a validation step of the mechanisms involved in pure Ni substrate, the extrapolation of the process to several Ni-based superalloys (René N5 (SX), CM-247 (DS), PWA- 1483 (SX) and IN-738LC (EQ)) revealed different coating compositions and microstructures. A particular attention was therefore paid onto the effect of alloying elements (Cr, Ta, Ti) as well as their segregation in the coating. The high temperature behaviour of the coated samples has been studied through isothermal oxidation (1000h in air between 900 and 1100°C) and showed that the oxidation and interdiffusion phenomena ruled the degradation mechanisms. Besides, the electrodeposition of ceria before the application of the PARTICOAT coating allowed to strongly limit interdiffusion phenomena and stabilized the nickel aluminide coating.

The significance of the radioxenon memory effect in the context of the International Monitoring System of the Comprehensive Nuclear-Test-Ban Treaty is introduced as motivation for the project. Existing work regarding xenon memory effect reduction and thin film diffusion barriers is surveyed. Experimental techniques for radioxenon production and exposure, as well as for thin film deposition on plastic by plasma enhanced chemical vapor deposition (PECVD), are detailed. A deposition rate of 76.5 nm min⁻¹ of SiO₂ is measured for specific PECVD parameters. Relative activity calculations show agreement within 5% between identically exposed samples counted on parallel detectors. Memory effect reductions of up to 59±1.8% for 900 nm SiO₂ films produced by plasma enhanced chemical vapor deposition and of up to 77±3.7% for 50 nm Al₂O₃ films produced by atomic layer deposition are shown. Future work is suggested for production of more effective diffusion barriers and expansion to testing in operational monitoring stations. / text

This thesis investigates surface coatings as xenon diffusion barriers on plastic scintillators. The motivation for the work is improved radioxenon detection systems, used within the verification regime of the Comprehensive Nuclear-Test-Ban Treaty (CTBT). One type of radioxenon detection systems used in this context is the Swedish SAUNA system. This system uses a cylindrical plastic scintillator cell to measure the beta decay from radioxenon isotopes. The detector cell also acts as a container for the xenon sample during the measurement. One problem with this setup is that part of the xenon sample diffuses into the plastic scintillator material during the measurement, resulting in residual activity left in the detector during subsequent measurements. This residual activity is here referred to as the memory effect. It is here proposed, and demonstrated, that it is possible to coat the plastic scintillator material with a transparent oxide coating, working as a xenon diffusion barrier. It is found that a 425 nm Al2O3 coating, deposited with Atomic Layer Deposition, reduces the memory effect by a factor of 1000, compared an uncoated detector. Furthermore, simulations show that the coating might also improve the light collection in the detector. Finally, the energy resolution of a coated detector is studied, and no degradation is observed. The focus of the thesis is measurements of the diffusion barrier properties of Al2O3 films of different thicknesses deposited on plastic scintillators, as well as an evaluation of the expected effect of a coating on the energy resolution of the detector. The latter is studied through light transport simulations. As a final step, a complete coated plastic scintillator cell is evaluated in terms of memory effect, efficiency and energy resolution. In addition, the xenon diffusion process in the plastic material is studied, and molecular dynamics simulations of the Xe-Al2O3 system are performed in order to investigate the reason for the need for a rather thick coating to significantly reduce the memory effect.

Ces travaux de thèse ont pour but de développer des cellules photovoltaïques à base de Cu(In,Ga)Se2 (CIGS) sur des substrats métalliques. L'objectif principal consiste à résoudre les différentes problématiques liées à l'utilisation de ces substrats (Ti et acier inoxydable) en s'appuyant sur une adaptation de l'électrode arrière. L'étude est focalisée sur l'élaboration de contacts arrière en Mo par pulvérisation cathodique. Dans un premier temps, des contacts arrières en monocouches et en bicouches sont comparés, démontrant les intérêts des structures en bicouches. Ces dernières sont obtenues en utilisant successivement deux pressions différentes pendant le dépôt du contact arrière. Nous montrons que la pression utilisée pendant le dépôt de la couche inférieure influe sur la morphologie de la couche supérieure. Il en résulte des modifications de l'orientation cristalline du CIGS et des performances photovoltaïques. Dans une seconde étude, la couche inférieure est déposée à partir d'une cible de molybdène contenant du sodium (Mo:Na) afin d'apporter du Na dans le CIGS. Les différences entre le Mo et le Mo:Na sont d'abord étudiées. Nous montrons ensuite que la diffusion du sodium vers le CIGS dépend de la pression de dépôt de la couche de Mo:Na. Dans le cas de substrats en Ti, des rendements équivalents aux substrats en verre sodo-calcique sont obtenus en utilisant le molybdène dopé au sodium. Nous montrons aussi qu'en présence de sodium, l'effet de la pression de dépôt de la couche inférieure sur les performances est minimisé. / This PhD work is focused on the development of Cu(In,Ga)Se2 (CIGS) solar cells on metallic substrates. The main goal is to fix various issues related to the replacement of the standard soda-lime glass substrates by metallic substrates (Ti and stainless steel foils), through optimizing and functionalizing of the back contact. Thus, the study is focused on the development of DC-sputtered Mo back contacts. First, monolayer-based and bilayer-based back contacts are compared, demonstrating the interests of the bilayers. The latter are obtained by successively using two different deposition pressures during the DC-sputtering of the back contact. We show that the deposition pressure of the bottom layer of the back contact influences the morphology of the top layer. This leads to changes in the cristallographic properties of the CIGS and in the global device performance. In a second study, the bottom layer is deposited using a Na-doped Mo sputtering target (Mo:Na), in order to use the back contact as a sodium precursor for the CIGS. The differences between the sputtered Mo and Mo:Na layers are first studied. Then, we show that sodium diffusion depends on the deposition pressure of the Mo:Na layer. On Ti substrates, conversion efficiencies as high as on the glass substrates were reached using the Mo:Na layers. It is also shown that when sodium is present, the effect of the deposition pressure of the bottom layer on the device performance is reduced.