Electrochromic properties of sputter-deposited nickel-based oxide films have been studied with a two-fold goal. From a practical point of view, the optical switching performance has been improved by optimizing the deposition conditions and film stoichiometry with respect to oxygen and hydrogen, and further by adding Mg, Al, Si, Zr, Nb or Ta to the films. From a theoretical point of view, details of the coloration mechanism have been studied by means of electrochemical intercalation (CV, GITT), optical measurements (UV, VIS, NIR and MIR), RBS, XRD, XPS and EXAFS. Optimization of deposition conditions has been illustrated by the example of films made by sputtering of a non-magnetic Ni(93)V(7) % wt. target in an atmosphere of Ar/O2/H2. The optimized films exhibit transmittance modulation between 20% and 75 % at 18 mC/cm2 charge intercalation. The remaining problem with nickel oxide and nickel vanadium oxide films is their residual yellow-brown color tint in the bleached state, which disappears as the short-wavelength transmittance increases upon addition of Mg, Al, Zr or Ta. Optimization of deposition conditions by co-sputtering from two targets and the film composition for mixed oxide films has been illustrated by the example of nickel aluminium oxide. The mechanisms of coloration upon electrochemical charge insertion and ozone exposure have been investigated. In the beginning of the electrochemical cycling, first, a reconstruction and crystallization is observed with the outer most part of the grain surface being transformed from oxygen rich nickel oxide into nickel oxy-hydroxide and hydroxide by transfer of H+ and OH- groups. After the charge capacity has been stabilized, only a transfer of H+ occurs with two reversible reactions involved: the first one from Ni(OH)2 to NiOOH and the second one from NiO and Ni(OH)2 to Ni2O3. Ozone coloration is described by a similar reaction scheme. The ozone molecule is split on the surface and dehydrogenates Ni(OH)2 into NiOOH. Further dehydrogenation produces Ni2O3 as in the electrochemical coloration.

This thesis treats the reflective and structural properties of multilayer structures. Soft X-ray multilayer mirrors intended as near-normal incidence reflective optics and polarizers in the water window (λ=2.4-4.4 nm) are the main focus. Such mirrors require multilayer periodicities between 1.2-2.2 nm, a large number ~600of multilayer periods (N), and atomically flat interfaces. Bi-metallic multilayers were deposited by dual-target magnetron sputtering on Si(001) Geometrical roughness and intermixing/interdiffusion at the interfaces were investigated in connection with the impact of ion-surface interactions during growth of Cr/Ti, Cr/Sc, and Ni/V multilayers. This was achieved by comparing multilayers grown with or without high-flux low energy (Eion<30 eV) ion assistance. The use of modulated ion assistance resulted in a substantial improvement of interface flatness and abruptness in each of theAb-initio calculations indicate that the stabilization of the amorphous layer structure is due to a lowering of the total energy of the system by eliminating high energy incoherent interfaces between crystalline Sc and Cr. Light element incorporation in Cr/Sc multilayers was investigated through residual gas pressure variation. It is shown that multilayers retain their structural and optical properties within the high vacuum range of 2×10-7-to-2×10-6 Torr. The incorporation of 34 at.% nitrogen at a higher residual gas pressure ( ~2×10-5 Torr) resulted in highly textured understoichiometricx/ScNy multilayers. As a result of nitrogen incorporation, interface widths as small as 0.29 nm, and near-normal incidence reflectivity enhancement (at λ=3.11 nm) by 100 % (compared to pure Cr/Sc multilayers) was achieved. Light element incorporation was also found to be advantageous for the thermal stability of the multilayers. In-situ hard X-ray reflectivity measurements performed during isothermal annealing in thex/ScNy are stable up to 350 °C. As an alternative route to metallic multilayers, single crystal CrN/ScN superlattices, grown by reactive sputtering in N atmosphere onto MgO(001), were also investigated. The superlattice synthesis at 735 °C, resulted in highly abrupt interfaces with minimal interface widths of 0.2 nm. As-deposited superlattices with only 61 periodsλ=3.11 nm as well as very high thermal stability up to 850 °C. / Denna avhandling behandlar syntes, analys, och materialvetenskap rörande så kallade multilagerspeglar för mjuk röntgenstrålning. Speglarna är lämpade som optiska komponenter för instrument såsom röntgenmikroskop i våglängdsområdet 2,4 nm till 4,4 nm, även kallat vattenfönstret. Tack vare de senaste decenniernas stora teknologiska och vetenskapliga framsteg i att framställa mycket intensiva källor för mjuk röntgenstrålning, såsom tex synkrotronljuskällor, frielektronlasrar, och plasmagenererade källor, är det nu tänkbart att utnyttja denna strålning till nya tillämpningar som tidigare inte varit möjliga. Några exempel är; röntgenmikroskopi av biologiska preparat med upplösning ca 1/100 av det som är möjligt med synligt ljus, fotolitografi av Det finns flera stora utmaningar för att lyckas tillverka multilagerspeglar. Först och främst måste man hitta materialkombinationer som ger upphov till reflektion i mellanytorna mellan materialen men som inte samtidigt absorberar all röntgenstrålning. Dessutom måste materialen gå att belägga på varandra i flera hundra tunna lager, vart och ett endast ca 1 nanometer tjockt, med en ytojämnhet om endast några tiondels nanometer. Den absoluta tjockleks precision i varje I det här arbetet har fyra olika typer av multilagerbeläggningar undersökts: krom/titan (Cr/Ti), krom/skandium (Cr/Sc), nickel/vanadin (Ni/V) samt kromnitrid/skandiumnitrid (CrN/ScN). Materialvalen har baserats på teoretiska beräkningar som visat att dessa materialsystem genererar mycket god reflektans i vattenfönstret. Varje kombination av metaller är optimal för en specifik våglängd och de individuella lagertjocklekarna måste optimeras teoretiskt för varje enskilt För Cr/Sc multilager har vi visat att lagren som beläggs har en oordnad, så kallad amorf, struktur mellan metallatomerna som har sitt ursprung i att multilagrets totala energi kan sänkas om mellanytor mellan kristallint Cr och kristallint Sc kan undvikas. Studier av effekterna av kväveupptag hos Cr/Sc multilagerspeglar under sputtringsprocessen har lett till ökad förståelse av materialsystemet. Till exempel har vi visat att kvävet framförallt binder till de inre regionerna av Sc och inte så mycket till Cr-lagren eller i mellanytorna. Med kväve i strukturen har vi gjort speglar som tål höga temperaturer, vilket är av stor betydelse för tillämpningar baserade högintensiva ljuskällor. Så kallade supergitter, dvs multilager

This thesis reports on synthesis, microstructure and properties of binary and ternary carbide thin films deposited by dc magnetron sputtering. These materials are interesting since they exhibit a wide range of useful properties, such as high hardness, resistance to wear and oxidation, and high electrical conductivity. Here, an early transition metal (M) and carbon (C) have been used as the basis, often with the addition of a second M-element or an A-group element (A). In these systems nanocomposites, metastable solid solutions, multilayers, or Mn+1AXn-phases have been deposited. The Mn+1AXn-phases are a group of nanolaminated compounds with a unique mixture of metallic and ceramic properties. In general X is carbon or nitrogen, although here only carbon has been used. Epitaxial MAX-phase thin films of Ti2AlC, Ti3AlC2 and V2GeC have been deposited for the first time. They have been studied with emphasis on phase stability, phase composition and nucleation characteristics to gain deeper insights into their growth. The microstructure of the films was characterized by electron microscopy and X-ray diffraction. In addition, bond strength characteristics have been studied by soft X-ray spectroscopy and complementary calculations within DFT. Their mechanical and electrical properties have been studied, and the results are discussed on the basis of their electronic structure. Furthermore, by interleaving the Ti3SiC2 MAX-phase with TiC0.67 a multilayer structure has been formed, for which a new intrusion-type deformation behaviour has been described. A new concept in the design of nanocomposite films has been developed, whereby a solid solution of a weak carbide-forming element in the carbide structure creates a driving force for surface segregation of C. This concept has been verified both theoretically and experimentally for the Ti-Al-C and Ti-Fe-C systems. It has been shown by pin-on-disc measurements that this surface segregation leads to graphitization and consequently a very low friction coefficient for these films. Finally, it has been demonstrated that low-friction films with tunable magnetic properties can be achieved in the Ti-Fe-C system.

A microphone has been used to measure the dynamic pressure inside a vacuum chamber during high power impulse magnetron sputtering with high enough time-resolution (~µs) to track the pressure change during the discharge pulse. An experimental measurement of the dynamic pressure is of interest since it would give information about gas depletion, which is believed to dramatically alter the plasma discharge characteristics. This investigation has shown that the magnitude of the pressure wave, which arises due to the gas depletion, corresponds to a 0.4 - 0.7Pa (3 - 5.5mTorr) pressure difference at a distance of 15cm from the target, with base pressures of 2 - 6mTorr for a peak current of 110A. It has also been shown that another pressure wave, about 250µs later, can be detected. Its explanation is suggested to be that the initial pressure wave is bouncing against the chamber walls and thereby causing another peak.

Current body armor technologies need further improvements in their design to help reduce combat injuries of military and law enforcement personnel. Kevlar-based body armor systems have good ballistic resistance up to a certain ballistic threat level due to limitations such as decreased mobility and increased weight [1,2]. Kevlar fibers have been modified in this work using a nano-scale boron carbide coating and a marked increase in the puncture resistance has been experimentally observed. It is hypothesized that this improvement is due to the enhancement of the mechanical properties of the individual Kevlar fibers due to the nano-scale coatings. This study presents a comprehensive experimental investigation of individual Kevlar fibers based on nanoindentation to quantify the cause of the enhanced puncture resistance. The experimental setup was validated using copper wires with a diameter size in the same order of magnitude as Kevlar fibers. Results from nanoindentation did not show significant changes in the modulus or hardness of the Kevlar fibers. Scanning Electron Microscopy revealed that the coated fibers had a marked change in their surface morphology. The main finding of this work is that the boron carbide coating did not affect the properties of the individual fibers due to poor adhesion and non-uniformity. This implies that the observed enhancement in puncture resistance originates from the interaction between fibers due to the increase in roughness. The results are important in identifying further ways to enhance Kevlar puncture resistance by modifying the surface properties of fibers.

Nickel based coatings were deposited on copper substrates by two different sputtering techniques from a nickel alloy based target. The substrates used were commercially available copper based substrates for low duty electrical contacts. The coatings were analyzed and evaluated as copper diffusion barriers for electrical contact applications. In addition two types of commercially available electroplated nickel coatings (referred to as type A electroplated coatings and type B electroplated coatings) were characterized for comparison. The Technique I sputtered coatings were deposited using three different substrate bias voltages and two different working gas pressures. The Technique II coatings were deposited using two different substrate bias voltages and two different working gas pressures. All sputtered coatings were deposited at a temperature of 200° C. The quality of the barriers was investigated by analyzing their composition, microstructure, stress, mechanical properties , and surface roughness. The results show that sputtered coatings have polycrystalline structures while the two plated films had (200) orientation and (111) orientation. Both plated coatings contained impurities that originate from chemicals used in the plating baths. The surface of the sputtered coatings reflects the substrate surface, while the electroplated samples on the same substrate (type A coatings) show a smooth mirror like surface and the type B electroplated coatings show a rough surface. Technique II sputtered coatings showed the highest hardness in the amount of 13 GPa, followed by electroplated type A coatings with a hardness of about 9 GPa while the Technique I coatings showed hardness of 6-8 GPa. All sputtered coatings exhibited compressive stress while the electroplated type A coatings exhibited tensile stress of almost twice the magnitude. In this study it is shown that sputtered nickel based coatings sputtered nickel based coatings are a promising more environmental friendly alternative to electroplated nickel coatings.

HfO2 is a popular replacement for SiO2 in modern CMOS technology. It is used as the gate dielectric layer isolating the transistor channel from the gate. For this application, certain material property demands need to be met, most importantly, a high static dielectric constant is desirable as this positively influences the effectiveness and reliability of the device. Previous theoretical calculations have found that this property varies with the crystal structure of HfO2; specifically, the tetragonal structure possesses the highest dielectric constant (~70 from theoretical calculations) out of all possible stable structures at atmospheric pressure, with the cubic phase a far second (~29, also calculated). Following the results from previous experimental work on the phase formation of sputtered HfO2, this study investigates the possibility of producing thin films of HfO2 with the cubic or tetragonal structure by the addition of nitrogen to a reactive sputtering process at various deposition temperatures. Also, a new physical vapor deposition method known as High Power Impulse Magnetron Sputtering (HiPIMS) is employed for its reported deposition stability in the transition zone of metal-oxide compounds and increased deposition rate. Structural characterization of the produced films shows that films deposited at room temperature with a low N content (~6 at%) are mainly composed of amorphous HfO2 with mixed crystallization into t-HfO2 and c-HfO2, while pure HfO2 is found to be composed of amorphous HfO2 with signs of crystallization into m-HfO2. At 400o C deposition temperature, the crystalline quality is enhanced and the structure of N incorporated HfO2 is found to be c-HfO2 only, due to further ordering of atoms in the crystal lattice. Optical and dielectric characterization revealed films with low N incorporation (< 6 at%) to be insulating while these became conductive for higher N contents. For the insulating films, a trend of increasing static dielectric constant with increasing N incorporation is found.

In this work, we investigate the relation between the diffusion behavior of Ti1-xAlxN at elevated temperatures and the microstructure. Thinfilm samples are synthesized by reactive co-sputtering with two cathodes. One cathode equipped with Ti target is connected to a highpower impulse magnetron sputtering (HiPIMS) power supply, and the other cathode equipped with Al target is operated with a directcurrent power source. The spinodal decomposition of cubic metastable Ti1-xAlxN controlled by thermally activated diffusion is observe fordiffusion behavior. Various HiPIMS pulsing frequencies are used to achieve different microstructure, while altered power applied to Altarget is used to change the Al content in films. In the phase composition analysis achieved by GI-XRD, the right-shift of (111) film peakalong with increasing Al-power is observed. A saturation of the right-shift and h-AlN peaks are also observed at certain Al-power. Thechemical composition determined by ERDA shows trends of reducing Al solubility limit in metastable phase and O contamination upondecreasing the pulsing frequency. More N deficiency is found in samples deposited with higher frequency. In the 500 Hz and 250 Hzsamples deposited into similar composition and thickness, no apparent difference of the microstructure is observed from the SEM crosssectionalimages. From HT-XRD, we observe higher intensity of TiO2 and h-AlN peaks in 500 Hz sample at elevated temperature ascompared with 250 Hz one. From the reduction of O contamination, denser Ti1-xAlxN films are able to be deposited with lower HiPIMSpulsing frequency. In addition, the higher intensity observed in HT-XRD patterns indicates that the 500 Hz sample is more open todiffusion and therefore allows the new formed phases to grow in larger grains.

High power impulse magnetron sputtering (HiPIMS) is a novel pulsed power technique. In HiPIMS, high power pulses are applied to the target for short duration with a low duty factor. It provides a high degree of ionization of the sputtered material (in some cases up to 90%) and a high plasma density (1019 m-3) which results in densification of the grown films. Recently a large side-transport of the sputtered material has been discovered, meaning that the sputtered material is transported radially outwards, parallel to the cathode surface. In this research, we use this effect and study the side-ways deposition of thin films. We designed a new magnetron sputtering system, consisting of two opposing magnetrons with similar polarity. Ti films were grown on Si using the side-ways transport of the sputtered material. Scanning electron microscope was employed to investigate the microstructure of the grown films. Optical emission spectroscopy (OES) measurements were made for investigating the ionized fraction of the sputtered material while Langmuir probe measurements were made for evaluating the plasma parameters such as electron density. The conclusion is that the system works well for side-ways deposition and it can be useful for coating the interior of cylindrically shaped objects. It is a promising technique that should be used in industry.

M-plane (101 ¡Â0) ZnO thin films were grown on m-plane sapphire (101 ¡Â0) substrates by RF magnetron sputtering. We varied the RF power, working pressure, and O2/Ar ratio to obtain the best growth conditions. Structural properties were investigated by X-ray diffraction(XRD). XRD measurements showed that the crystal orientation of ZnO films was non-polar m-plane (101 ¡Â0). In addition, photoluminescence (PL) spectrum showed the bandgap energy of ZnO films was about 3.24 eV. PL spectrum showed zinc vacancy signal for films grown in oxygen rich condition. Carrier concentration was measured by hall measurement as well as FTIR spectrometry. The results showed the carrier concentration calculated by optical measurements was higher than hall measurements. One possibility for this could be the band tail at the bottom of conduction band. This band tail can make the effective mass larger and thus influencing the optical carrier concentration.