In this thesis, research on synthesis, structure and characterization of amorphous carbide-based thin films is presented. Crystalline and nanocomposite carbide films can exhibit properties such as high electrical conductivity, high hardness and low friction and wear. These properties are in many cases structure-related, and thus, within this thesis a special focus is put on how the amorphous structure influences the material properties. Thin films within the Zr-Si-C and Cr-C-based systems have been synthesized by magnetron sputtering from elemental targets. For the Zr-Si-C system, completely amorphous films were obtained for silicon contents of 20 at.% or higher. Modeling of these films, as well as experimental results suggest that the films exhibit a network-type structure where the bond types influence the material properties. Higher hardness and resistivity were observed with high amounts of covalent Si-C bonds. Several studies were performed in the Cr-C-based systems. Cr-C films deposited in a wide composition range and with substrate temperatures of up to 500 °C were found to be amorphous nanocomposites, consisting of amorphous chromium carbide (a-CrCx) and amorphous carbon (a-C) phases. The carbon content in the carbidic phase was determined to about 30-35 at.% for most films. The properties of the Cr-C films were very dependent of the amount of a-C phase, and both hardness and electrical resistivity decreased with increasing a-C contents. However, electrochemical analysis showed that Cr-C films deposited at higher substrate temperature and with high carbon content exhibited very high oxidation resistance. In addition, nanocomposite films containing Ag nanoparticles within an amorphous Cr-C matrix were studied in an attempt to improve the tribological properties. No such improvements were observed but the films exhibited a better contact resistance than the corresponding binary Cr-C films. Furthermore, electrochemical analyses showed that Ag nanoparticles on the surface affected the formation of a stable passive film, which would make the Cr-C/Ag films less resilient to oxidation than the pure Cr-C films.

This poster was presented in the Materials for Advanced Metallization (MAM) 2014 Conference in Chemnitz, Germany. Abstract: Atomic Layer Deposition (ALD) has emerged as an ubiquitous method for the deposition of conformal and homogeneous ultra-thin films on complex topographies and large substrates in microelectronics. Electrochemical deposition (ECD) is the first choice for the deposition of copper (Cu) into the trenches and vias of the interconnect system for ULSI circuits. The ECD of Cu necessitates an electrically conductive seed layer for filling the interconnect structures. ALD is now considered as a solution for conformal deposition of Cu seed layers on very high aspect ratio (AR) structures also for technology nodes below 20 nm, since physical vapor deposition is not applicable for structures with high AR. Cu seed layer deposition by the reduction of Cu2O, which has been deposited from the Cu(I) β-diketonate precursor [(nBu3P)2Cu(acac)], has been successfully carried out on different substrates like Ta, TaN, SiO2, and Ru [1, 2]. However, still many questions are unanswered regarding the underlying surface chemistry of the precursor on many substrates, leading to different growth modes during ALD. In this work, the surface chemistry of [(nBu3P)2Cu(acac)] on SiO2 substrate is investigated by in-situ X-ray photoelectron spectroscopy (XPS), reporting vital information about the oxidation state and the atomic concentration after chemisorption on the substrates kept at different temperatures. The aim of the investigation is to understand the stepwise change in the precursor oxidation state with increasing substrate temperature and to identify the temperature limit for the thermal ALD with this Cu precursor on SiO2. For the experiments, the Cu precursor was evaporated on SiO2 substrates kept at temperatures between 22 °C and 300 °C. The measured C/Cu and P/Cu concentration indicated that most of the nBu3P ligands were released either in the gas phase or during adsorption (Fig. 1a). No disproportionation was observed for the Cu precursor in the temperature range between 22 °C and 145 °C. Similarly, in this temperature range the Auger parameter calculated from Cu 2p3/2 and Cu L3VV spectra was found to be 360.0±0.2 eV, comparable to Cu(I) oxidation state [3]. However, disproportionation of the Cu precursor was observed above 200 °C, since C/Cu concentration ratio decreased and substantial metallic Cu was present on the substrate. Hence, 145 °C is the temperature limit for the ALD of Cu2O from this precursor, as the precursor must not alter its chemical state after chemisorption on the substrate. 500 ALD cycles with the probed Cu precursor and wet O2 as co reactant were carried out on SiO2 at 145 °C. After ALD, in situ XPS analysis confirmed the presence of Cu2O on the substrate. Ex-situ spectroscopic ellipsometry indicated an average film thickness of 2.5 nm of Cu2O deposited with a growth per cycle of 0.05 Å/cycle, comparable to previous experiments. References: [1] T. Waechtler, S. Oswald, N. Roth, A. Jakob, H. Lang, R. Ecke, S. E. Schulz, T. Gessner, A. Moskvinova, S. Schulze, M. Hietschold, J. Electrochem. Soc., 156 (6), H453 (2009). [2] T. Waechtler, S. -F. Ding, L. Hofmann, R. Mothes, Q. Xie, S. Oswald, C. Detavernier, S. E. Schulz, X. -P. Qu, H. Lang, T. Gessner, Microelectron. Eng., 88, 684 (2011). [3] J. P. Espinós, J. Morales, A. Barranco, A. Caballero, J. P. Holgado, A. R. González Elipe, J. Phys. Chem. B, 106, 6921 (2002).

Our aim was to establish a methodology for laser assisted oxidation of semiconductor and metal surfaces. One advantage of laser oxidation is the fact that radiation is heavily absorbed in a thin surface layer of the sample and the other is its ability for local oxidation. In addition to this, laser beam can be directed into some areas that other processes cannot reach. For these reasons, Nd:YAG pulsed laser working at 1064 nm wavelength is used for the oxidation purposes of Si and Ta films. First, SiO2 layer was obtained for various O2 pressures and laser powers. The thickness, refractive index, structural, dielectric, electrical and optical characteristics of the SiO2 layers have been determined. We have established that there exists an interval of laser power in which the oxidation occurs without surface melting. The oxidation process is controlled by the laser power rather than by the substrate temperature (673 &ndash / 748 K). It was found that better film quality is obtained at higher substrate temperatures and laser power greater than 3.36 J/cm2. Second, rf-sputtered Ta films were oxidized by laser, because Ta2O5 appears to be a good promising candidate to replace SiO2 because of its high dielectric constant, high breakdown voltage and relevant small leakage current values. It was found that the substrate temperature is an important parameter to obtain denser layers with reduced amount of suboxides and the most suitable substrate temperature range is around 350 C to 400 C. &amp / #946 / -orthorhombic crystal structure was obtained when the substrate temperature is 350 &ndash / 400 C for thinner films (up to 20 &ndash / 25 nm) and 300 &ndash / 350 C for thicker films (40 nm). The refractive index values of laser grown thin tantalum oxide films were between ~1.9 and 2.2 being close to those of bulk Ta2O5 (2.0 &ndash / 2.2). Oxide thicknesses in uniform Gaussian&ndash / like shapes were measured as around the twice of those initial Ta films. Effective dielectric constant values reached ~26 when the substrate temperature was increased from 250 C to around 400 C. It was shown that the leakage current density level decreases with increasing substrate temperature. However, the refractive index values of the films were smaller than those of thermally grown films. Porous structure formed during laser oxidation might be the reason for lower refractive indices and can be improved by post&ndash / oxidation annealing.

An experimental and theoretical approach is taken to determine the effect of a heterojunction on the effective work function in a metal/high-? gate stack, the characteristics of aqueous hydrochloric acid cleaned (aq-HCl) GaN surface and the interface between GaN and Al2O3, HfO2 and GaON. The investigation of the effect of a heterojunction on the effective work function in a metal/high-? gate stack found that when a Ge/Si heterostructure on silicon is lightly doped and sufficiently thin, the work function can be extracted in a manner similar to that for a simple silicon substrate. Modifications to the terraced oxide structure are proposed to remove oxidation effects of the alternate channel materials. The extracted work function of TiN with various thicknesses on HfSiO is found to be in agreement with that of TiN on a silicon substrate. X-ray and ultraviolet photoelectron spectroscopy are used to observe the interface electronic states at the GaN (0001) and Al2O3, HfO2 and GaON dielectric interfaces. The GaN is cleaned using aqueous HCl prior to thermal oxidation to form GaON and atomic layer deposition of Al2O3 and HfO2. This was followed by a post deposition anneal. The GaN/HfO2 and GaN/Al2O3 interfaces exhibited dipoles of 1.6 eV and 0.4 eV +/- 0.2 eV, respectively. It is determined that the formation of an interfacial layer at the GaN/HfO2 interface is the primary cause of the larger dipole. Due to the knowledge of the formation of an interfacial GaOx or GaON layer during atomic layer deposition of HfO2, a better understanding of the GaN/GaON interface is needed. To accomplish this task, the interface electronic states at the GaN(0001) and GaON interface are observed using X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). XPS and UPS analysis of the GaN/GaON interface resulted in the calculation of a -2.7 eV +/- 0.2 eV dipole assuming that the core level shifts are only representative of the GaN band bending at the interface. If it is assumed that the core level shifts are only due to the oxidation of GaN, then the exhibited dipole at the GaN/GaON interface is -1.8 eV +/- 0.2 eV. Results indicate that the observed dipole is primarily caused by the polarization of the GaN. A theoretical approach is taken to provide a more complete understanding of the underlying formation mechanisms of a GaON interfacial layer during atomic layer deposition of HfO2. First, density functional theory is used to calculate the interactions of oxygen and water with the Ga-face of GaN clusters. The GaN clusters could be used as testbeds for the actual Ga-face on GaN crystals of importance in electronics. The results reveal that the local spin plays an important role in these interactions. It is found that the most stable interactions of O2 and the GaN clusters results in the complete dissociation of the O2 molecule to form two Ga-O-Ga bonds, while the most stable interactions between a H2O molecule and the GaN clusters are the complete dissociation of one of the O-H bonds to form a Ga-O-H bond and a Ga-H bond. Second, density functional theory is used to calculate the interaction of the reactants used to deposit HfO2 and Al2O3 during atomic layer deposition with hydrolyzed Ga-face GaN clusters. The results suggest that while further research is needed in this area to grasp a better understanding of the interactions of Trimethylaluminum (TMA) or Tertrakis(EthylMethylAmino)Hafnium (TEMAH) with hydrolyzed GaN clusters, it is found that a Ga-N(CH3)(CH2CH3) bond can form during the deposition of HfO2 using ALD and TEMAH as the reactant without breaking the Hf-N bond. The formation of a Ga-N(CH3)(CH2CH3) bond is significant because with the introduction of water into the system, the methyl and ethylmethyl groups may react to form a Ga-N-O bond which is believed to be the interfacial oxide found during deposition of HfO2 using ALD on GaN. No Ga-C bond structure formed in any fully optimized stable structure when analyzing the interaction of TMA with hydrolyzed GaN.

The physical properties of the protective passive films formed on the surface of stainless steels under electrochemical polarization in different electrolytes were studied. The structure of these films was analyzed as a function of depth using photoelectron spectroscopy (PES). Depth profiling (using PES) of the surface layer was achieved by either changing the angle of incidence to achieve different analysis depths (ARXPS), by argon ion etching, or by varying the energy of the incoming x-rays by the use of synchrotron radiation. The use of hard x-rays with high resolution (HAXPES) provided novel quantified information about the nickel content underneath the passive films. A complex environment was found in these surface layers composed of an outermost monolayer of iron on top of a layer of chromium hydroxides covering an underlayer of chromium oxides. Molybdenum was enriched in the interface between the metal and oxide. Nickel is enriched underneath the passive film and therefore nickeloxides are only present in the surface layer in low concentrations. A comparison was performed on austenitic and duplex stainless prepared by hot isostatically pressed (HIP) or cast and forged processes. HIP stainless steel was produced using the burgeoning technique of pressing gas atomized powders together. The structure of these steels is far more homogenous with a lower porosity than that of the conventionally prepared equivalents. It was shown that hot HIP austenitic steel had better pitting corrosion resistance than its conventional counterpart. Finally, the duplex steel was cycled in a Li-ion battery to explore its potential application as a current collector. It was shown that the passive film formed in the organic solvents is similar in composition and thickness to the films formed in aqueous solutions. However, it is doubtful if steel could be used as current collector in batteries due to its high reactivity with lithium.

Electrochemical behavior of electrolytic manganese dioxide (EMD), chemically prepared battery grade manganese dioxide (BGM), titanium dioxide (TiO2), lithium iron phosphate (LiFePO4) and lithium manganese phosphate (LiMnPO4) in aqueous lithium hydroxide electrolyte has been investigated. These materials are commonly used as cathodes in non-aqueous electrolyte lithium batteries. The main aim of the work was to determine how the electroreduction/oxidation behavior of these materials in aqueous LiOH compares with that reported in the literature in non-aqueous electrolytes in connection with lithium batteries. An objective was to establish whether these materials could also be used to develop other battery systems using aqueous LiOH as electrolyte. The electrochemical characteristics of the above materials were investigated by subjecting them to slow scan cyclic voltammetry and determining the charge/discharge characteristics of Zn/cathode material-aqueous LiOH batteries. The products of electroreduction/oxidation were characterized by physical techniques using X-ray diffraction (XRD), scanning electron micrography (SEM), X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), Thermogravimetric analysis (TG) and infra-red spectrometry (IR). The reduction of ã-MnO2 (EMD) in aqueous lithium hydroxide electrolyte is found to result in intercalation of Li+ into the host structure of ã-MnO2. The process was found to be reversible for many cycles. This is similar to what is known to occur for ã-MnO2 in non-aqueous electrolytes. The mechanism, however, differs from that for reduction/oxidation of ã-MnO2 in aqueous potassium hydroxide electrolyte. KOH electrolyte is used in the state-of-art aqueous alkaline Zn/MnO2 batteries. Alkaline batteries based on aqueous KOH as the electrolyte rely upon a mechanism other than K+ intercalation into MnO2. This mechanism is not reversible. This is explained in terms of the relative ionic sizes of Li+ and K+. The lithium-intercalated MnO2 lattice is stable because Li+ and Mn4+ are of approximately the same size and hence Li+ is accommodated nicely into the host lattice of MnO2. The K+ ion which has almost double the size of Li+ cannot be appropriately accommodated into the host structure and hence the K+ -intercalated MnO2 phase is not stable. Chemically prepared battery grade MnO2 (BGM) is found to undergo electroreduction/oxidation in aqueous LiOH via the same Li+ intercalation mechanism as for the EMD. While the Zn/BGM- aqueous LiOH cell discharges at a voltage higher than that for the Zn/EMD- aqueous LiOH cell under similar conditions, the rechargeability and the material utilization of the BGM cell is poorer. The cathodic behavior of TiO2 (anatase phase) in the presence of aqueous LiOH is not reversible. In addition to LiTiO2, Ti2O3 is also formed. The discharge voltage of the Zn/TiO2- aqueous LiOH cell and material utilization of the TiO2 as cathode are very low. Hence TiO2 is not suitable for use in any aqueous LiOH electrolyte battery. LiFePO4 (olivine-type structure) as a cathode undergoes electrooxidation in aqueous LiOH forming FePO4. However the subsequent reduction forms not only the original LiFePO4 but also Fe3O4. Thus the process is not completely reversible and hence LiFePO4 is not a suitable material for use as a cathode in aqueous battery systems. LiMnPO4 (olivine-type structure) undergoes reversible electrooxidation in aqueous LiOH forming MnPO4. The charge/discharge voltage profile of the Zn/MnPO4-aqueous LiOH cell, its coulombic efficiency and rechargeability are comparable to that of the cell using ã-MnO2. EMD and LiMnPO4 both have the potential for use in rechargeable batteries using aqueous LiOH as the electrolyte. Recommendations for further developmental work for such batteries are made.

Novel type of catalyst for proton exchange membrane fuel cells anode is demonstrated. It is based on magnetron sputtered Pt-CeO2 a Pt-Sn-CeO2 mixed oxides. It is shown, that these materials allow to significantly decrease amount of platinum in the anode catalyst. The preparation method yields high amount of platinum in ionized form, especially Pt2+ , which is related to the high activity. Stability of these catalytic layers were investigated under conditions similar to fuel cell anode (humidified hydrogen at elevated temperature). Also interaction of hydrogen a water under UHV conditions were studied, demonstrating high stability of the Pt2+ species. In the last part of the work sputtered Pt-Co mixed catalyst were investigated to be used in the PEMFC cathode. It is demonstrated that at right conditions, the sputtered alloy catalyst improves mass activity on cathode by factor more than two.

The world energy and product consumption keep increasing steadily over the years as the world population keeps growing and more countries become industrialized. As the world reserves deplete it becomes a necessity to find an alternative way to meet the population’s demand. Biomass conversion seems to be the future of a clean and sustainable world. Lignin is the second most abundant polymer in the biomass. Given the unique structure and chemical properties of lignin, a wide variety of bulk and fine chemicals can be obtained and be used for goods and biofuels production. Catalysis, with its selective bond cleavage and lower energy activation, is considered as a potential key solution in the process of lignin conversion into valuable chemicals. To gain insights into that catalytic system, we performed surface science experiments (X-ray Photoelectron Spectroscopy, Temperature Programmed Desorption and Reflection Absorption Infrared Spectroscopy) under Ultra-High Vacuum conditions (UHV). Due to lignin’s physical properties limitation under UHV conditions, lignin models with the same chemical structure such as phenol, anisole, 2-phenoxyethanol and veratrol were used to gain a better understanding of the reactivity of lignin itself. Dosing anisole and 2-phenoxyethanol on Pt(111) surprisingly gave benzene, carbon monoxide and hydrogen as the main desorbing products of decomposition. With the help of Density Functional Theory (DFT), we successfully explain the unexpected selectivity. In the present work, we show in particular that phenoxy PhO stands as a key intermediate. Although the UHV conditions do not allow the hydrogenation of phenoxy into phenol, i.e. the catalytic product, they reveal the key role of both hydrogen and carbonaceous species. Under UHV conditions, anisole and 2-phenoxyethanol are extensively dehydrogenated: it results in the formation of carbonaceous fragments, which can actually perform the deoxygenation of phenoxy into benzene. The reactivity of veratrol on Pt(111) hindered the formation of benzene and only gave carbon monoxide and hydrogen as the main desorbing products of decomposition. Although carbonaceous fragments were formed on the surface, the deoxygenation of the two oxygenated arm moieties does not occur without the total decomposition of the aromatic ring, hence the formation of coke. This detailed work opens the door to a rational design of metal-based catalysts and a route towards lignin valorization.

In linear accelerator driven 4th generation Free Electron Lasers (FELs), the final beam quality is set by the linac and ultimately by its photoinjector and photocathode. Therefore, to deliver cutting-edge beam characteristics, there are stringent requirements for the photocathode used in the photoinjector. Understanding how surface properties of materials influence photocathode properties such as quantum efficiency (QE) and intrinsic emittance is critical for such sources. Metal photocathode research at Daresbury Laboratory (DL) is driven by our on-site accelerators VELA (Versatile Electron Linear Accelerator) and CLARA (Compact Linear Accelerator for Research and Applications), a free electron laser test facility. Metals offer the advantage of a fast response time which enable the generation of short electron pulses. Additionally, they are robust to conditions within the gun cavity. The main challenge with metal photocathodes is to maximise their (relatively) low electron yield. In this PhD thesis, the goal has been to carry out an experimental investigation on alternative metals to copper, correlating surface properties with photoemissive properties. A range of surface analysis techniques have been employed: surface composition was investigated using X-ray Photoelectron Spectroscopy and Medium Energy Ion Scattering, Kelvin Probe apparatus and Ultra-violet Photoelectron Spectroscopy were used to measure work function, and Atomic Force Microscopy and Interferometric microscope provided images characterising surface morphology. The photocathode properties studied include: QE measured using a 265 nm UV LED source that was later upgraded to a 266 nm UV LASER, and Mean Transverse Energy measured using the Transverse Energy Spread Spectrometer. As a result of this work, Mg, Nb, Pb, Ti and Zr have all been identified as photocathode candidate materials, each exhibiting a QE greater than Cu. Additionally, surface preparation procedures for optimising QE from a selection of metals has been explored; the findings of these experiments would suggest that ex-situ Ar plasma treatment followed by in-situ heat treatment is well suited to remove surface contaminants without altering the surface morphology of the cathode. As part of this work, metallic thin films produced by magnetron sputtering have been produced; ultimately the chosen cathode metal will be deposited onto a cathode plug which will be inserted into the electron gun that will drive CLARA. Thus the preparation of metal thin films has been investigated and the effect of different substrate materials on the film properties has been explored. Preliminary experiments studying the effects of surface roughness on photoelectron energy distribution have been conducted; the findings have not been conclusive, thus further systematic studies are required.

La biocompatibilité d'un implant est principalement contrôlée par l'interface entre le biomatériau et le tissu environnant. Afin de contrôler cette interaction et de favoriser l'adhésion des cellules sur l'implant, nous avons créé à la surface d'alliages de titane des domaines nanométriques concentrés en séquence Arginine-Glycine-Acide Aspartique (RGD) reconnue pour ses propriétés adhésives. Après avoir modifié la chimie de surface par un agent de liaison aminosilane, nous avons utilisé les méthodes de synthèse de dendrimères ou liés des nanoparticules à l'aminosilane afin de démultiplier le nombre de amines primaires par site. Ces amines primaires étant ensuite utilisées pour attacher la séquence RGD à la surface du matériau. L'adhésion d'ostéoblastes sur les matériaux préparés a été étudié par acoustique picoseconde. / Abstract