In the process of sputtering, what a system operator concerns are the sputtering rate, target utilization, and substrates uniformity. All of them are influenced by variables such as electromagnetic environment, chamber temperature, and pressure. In thin film manufacturing, targets bombarded by ions will sputter atoms to the substrates in order to make thin films; therefore, when a certain target zone is extensively bombarded by ions, target surface will become thinner. In general, when certain part of the target is penetrated, it is no longer usable while utilization rate only from 30 to 50 percent. It causes considerable waste and relatively higher costs. As a result, the objective of this study is to enhance target utilization and the sputtering rate through appropriate adjustment in the structure of the existing DC Magnetron Sputtering System (MSS). Since, the magnetic field distribution in the chamber will be appropriately adjusted inside the DC MSS with extra iron annulus and active compensation magnetizations being added. However, in order to get the better structural refinement of DC MSS it needs a thorough design and management based on Taguchi Method. Then, based on such structural adjustment, electron trajectories on top surface of targets can be conveniently controlled, and target erosion patterns and the number of ions bombarding the target will be indirectly controlled. It will, as a result, achieve the objective of this study by enhancing not only the target utilization efficiency but the sputtering rate.

Le but de ce travail est de développer et de caractériser une nouvelle génération de revêtements multicouches anti-usure et anticorrosif à base de nitrure de chrome. A cause des conditions de sollicitations sévères auxquelles les outils de coupe sont soumis en plus des enjeux environnementaux liés à l’utilisation des fluides de coupe lors de l’usinage du bois, les monocouches qui constituent notre système multicouches doivent présenter des caractéristiques spécifiques. De ce fait, des couches minces de Cr, CrN et CrAlN ont été déposées sur un acier à outils de coupe du bois et sur des substrats de siliciums par pulvérisation magnétron réactive DC. Nous nous sommes intéressés dans un premier temps à optimiser les monocouches. Ensuite, ces revêtements ont été associés pour élaborer des multicouches Cr/CrN/CrAlN qui ont alors été caractérisées. Nous avons étudié les propriétés physico-chimiques, mécaniques, tribologiques et le comportement à la corrosion de différents revêtements multicouches. Les résultats obtenus indiquent que l’application d’un revêtement multicouches pouvait apporter des améliorations considérables à la résistance à l’usure et à la corrosion des outils de coupe du bois. / The aim of this study was to develop and characterize a new generation of wear and corrosion resistant multilayers Cr-N based coatings. Due to the severe conditions that wood cutting tools are subjected in addition to the environmental issue associated with the use of cutting fluids during wood machining, the monolayers that constitute our multilayers system must have specific characteristics. As a result, thin layers of Cr, CrN and CrAlN have been deposited on wood cutting tools steel and silicon substrates by DC reactive magnetron sputtering to be optimized. Then, the optimal monolayerscoatings were combined to develop the Cr/CrN/CrAlN multilayers. that were characterized to determine their physicochemical, mechanical, tribological properties and their corrosion behavior. The results obtained indicated that the application of a multilayer coating can greatly improve the wear and corrosion resistance of a wood cutting tools steel.

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.

This report describes the growth and characterization of thin amorphous samarium-cobalt alloy films. The samarium-cobalt alloy was grown by DC magnetron sputtering in the presence of an external magnetic field parallel to the thin film. The external magnetic field induces a uniaxial in-plane magnetic anisotropy in the samarium-cobalt alloy. The thin films were characterized with x-ray scattering, and the magnetic anisotropy was characterized with the magneto optic Kerr effect. The measurements showed a uniaxial in-plane magnetic anisotropy in the samarium-cobalt alloy films. It is not clear how amorphous the samples really are, but there are indications of crystalline and amorphous areas in the alloys.

In this thesis research on synthesis, microstructure and properties of carbide-based coatings is reported. These coatings are electrically conducting, and can be tailored for high hardness, low friction and wear, along with load-adaptive behaviour. Tailoring these properties is achieved by controlling the relative phase content of the material. Coatings have been synthesised by dc magnetron sputtering, and their structures have been characterised, mainly by X-ray photoelectron spectroscopy and X-ray diffraction. It has been shown that nanocomposites comprising of a nanocrystalline transition metal carbide (nc-MeCx, Me = Ti, Nb or V) and an amorphous carbon (a-C) matrix can result in low contact resistance in electrical contacts. Such materials also exhibit low friction and high resistance to wear, making them especially suitable for application in sliding contacts. The lowest contact resistance is attained for small amounts of the amorphous carbon phase. It has been shown that specific bonding structures are present in the interface between nc-TiCx and the a-C phases in the nanocomposite.  It was found in particular that Ti3d and C2p states are involved, and that considerable charge transfer occurs across the interface, thereby influencing the structure of the carbide. Further design possibilities were demonstrated for TiCx-based nanocomposites by alloying them with weakly carbide-forming metals, i.e., Me = Ni, Cu or Pt.  Metastable supersaturated solid solution carbides, (T1-xMex)Cy, were identified to result from this alloying process. The destabilisation of the TiCx-phase leads to changes in the phase distribution in the deposited nanocomposites, thus providing further control over the amount of carbon phase formed. Additional design possibilities became available through the decomposition of the metastable (Ti1-xMex)Cy phase through an appropriate choice of annealing conditions, yielding either more carbon phase or a new metallic phase involving Me. This alloying concept was also studied theoretically for all 3d transition metals using DFT techniques. It has also been demonstrated that Ar-ion etching (commonly used in the analysis of carbide based nanocomposites) can seriously influence the result of the analysis, especially for materials containing metastable phases. This implies that more sophisticated methods, or considerable care are needed in making these analyses, and that many of the earlier published results could well be in error.

Global warming and developments of alternative energy technologies have become important issues nowadays. Subsequently, the concept of energy harvesting is rising because of its ability of transferring waste energy into usable energy. Thermoelectric devices play a role in this field since there is tremendous waste heat existing in our lives, such as heat from engines, generators, stoves, computers, etc. Thermoelectric devices can extract the waste heat and turn them into electricity. Moreover, the reverse thermoelectric phenomenon has the function of cooling which can be applied to refrigerator or heat dissipation for electronic devices. However, the energy conversion efficiency is still low comparing to other energy technologies. The efficiency is judged by thermoelectric figure of merit (ZT), defined by Seebeck coefficient, electrical conductivity and thermal conductivity. In order to improve ZT, thin film materials are good candidates because of their structural effects on altering ZT.    Ca3Co4O9 thin films grown by reactive radio frequency magnetron sputtering followed by post-annealing process is studied in this thesis. Structural properties of the films with the evolution of elemental ratio (Ca/Co) of calcium and cobalt have been investigated. For the investigations, three samples having elemental ratio 0.82, 0.72, and 0.66 for sample CCO1, CCO2 and COO3, respectively, have been prepared. Structural properties of the films have been investigated by X-ray diffraction (XRD) θ-2θ and pole figure analyses. Surface morphology of the films has been investigated by scanning electron microscopic (SEM) analyses. The highly oriented and phase pure epitaxial Ca3Co4O9 thin films were obtained in the end.   Mixing of ScN and CrN to obtain ScxCr1-xN solid solution thin films by DC magnetron sputtering is the other task in this thesis. Growth of ScN and CrN thin films were studied first in order to get the best mixed growth conditions. The phase shifts between ScN (111) and CrN (111) peaks were observed in mixed growth films by XRD θ-2θ measurements, indicating the formation of ScxCr1-xN. Surface morphology of the films were investigated by SEM. The (111)-oriented ScxCr1-xN thin films with decent surface smoothness grown by DC magnetron sputtering at 600 °C in pure nitrogen with bias were developed.

Thin film cadmium telluride (CdTe) technology is the most important competitor for silicon (Si) based solar cells. Pulsed direct current (DC) magnetron sputtering is a new technique has been developed for thin film CdTe deposition. This technique is industrially scalable and provides uniform coating. It is also possible to deposit thin films at low substrate temperatures. A series of experiments are presented for the optimisation of the cadmium chloride (CdCl2) activation process. Thin film CdTe solar cells require CdCl2 activation process to improve conversion efficiencies. The role of this activation process is to increase the grain size by recrystallisation and to remove stacking faults. Compaan and Bohn [1] used the radio-frequency (RF) sputtering technique for CdTe solar cell deposition and they observed small blisters on CdTe layer surface. They reported that blistering occurred after the CdCl2 treatment during the annealing process. Moreover, void formation was observed in the CdTe layer after the CdCl2 activation process. Voids at the cadmium sulphide (CdS)/CdTe junction caused delamination hence quality of the junction is poor. This issue has been known for more than two decades but the mechanisms of the blister formation have not been understood. One reason may be the stress formation during CdTe solar cells deposition or during the CdCl2 treatment. Therefore, the stress analysis was performed to remove the defects observed after the CdCl2 treatment. This was followed by the rapid thermal annealing to isolate the CdCl2 effect by simply annealing. Small bubbles observed in the CdTe layer which is the first step of the blister formation. Using high resolution transmission electron microscopy (HR-TEM), it has been discovered that argon (Ar) working gas trapped during the deposition process diffuses in the lattice which merge and form the bubbles during the annealing process and grow agglomeration mainly at interfaces and grain boundaries (GBs). Blister and void formation were observed in the CdTe devices after the CdCl2 treatment. Therefore, krypton (Kr), neon (Ne) gases were used as the magnetron working gas during the deposition of CdTe layer. The results presented in this thesis indicated that blister and void formation were still existing with the use of Kr an Ne. Xe, which has a higher atomic mass than Kr, Ne, Ar, Cd and Te, was used as the magnetron working gas and it resulted in surface blister and void free devices.

This thesis reports on the development of low-temperature processes for transition metal carbide and MAX-phase thin film growth. Magnetron sputtering and evaporation, far from thermodynamical equilibrium, have been utilised to engineer the properties of the films by physical and chemical control. Deposition of W, W2C and β-WC1-x films with controlled microstructure, from nanocrystalline to epitaxial, is shown in the W-C system down to 100 oC. W films with upto 20 at% C exhibited an extreme solid-solution hardening effect, with a nanoindentation hardness maximum of 35 GPa. Furthermore, the design of epitaxial ternary carbide films is demonstrated in the Ti1-xVxCy system in the form of controlled unit-cell parameters, strain-free films with a perfect match to the substrate, and ternary epitaxial gradient films. Moreover, phase stabilisation and pseudomorphic growth can be tuned in (Nb,Mo)C and (Ti,W)C films. The results obtained can be used for example to optimise electrical contacts in SiC high-power semiconductor devices. A large part of this thesis focuses on the deposition of MAX-phases. These compounds constitute a family of thermally stable nanolaminates with composition Mn+1AXn, n=1, 2 or 3, where M is an early transition metal, A is generally a group 13-14 element, and X is C or N. They show a combination of typical ceramic and metallic properties and are also machinable by virtue of the unique deformation behaviour observed only in laminates. So far, the MAX-phases have almost exclusively been prepared by high-temperature sintering and studied in bulk form. However, this thesis establishes a patented seed layer approach for successful MAX-phase thin film depositions down to 750 oC. For the first time, single-phase and epitaxial films of Ti3SiC2, Ti3AlC2 and Ti2AlC have been grown. The method has also been used to synthesise a new MAX-phase, Ti4SiC3. In addition, two previously unreported intergrown MAX-type structures are presented, Ti5Si2C3 and Ti7Si2C5. Combined theoretical and experimental results show the possibility to deposit films with very low bulk resistivity and designed mechanical properties. Furthermore, the demonstration of MAX-phase and carbide multilayer films paves the way for macrostructure engineering, for example, in coatings for low-friction or wear applications.

Ag is a widely used electrical contact material due to its excellent electrical properties. The problems with Ag are that it is soft and has poor tribological properties (high friction and wear in Ag/Ag sliding contacts). For smart grid applications, friction and wear became increasingly important issues to be improved, due to much higher sliding frequency in the harsh operation environment. The aim of this thesis is to explore several different concepts to improve the properties of Ag electrical contacts for smart grid applications. Bulk Ag-X (X=Al, Sn In) alloys were synthesized by melting of metals. An important result was that the presence of a hcp phase in the alloys significantly reduced friction coefficients and wear rates compared to Ag. This was explained by a sliding-induced reorientation of easy-shearing planes in the hexagonal structure. The Ag-In system showed the best combination of properties for potential use in future contact applications.  This thesis has also demonstrated the strength of a combinatorial approach as a high-throughput method to rapidly screen Ag-based alloy coatings. It was also used for a rapid identification of optimal deposition parameters for reactive sputtering of a complex AgFeO2 oxide with narrow synthesis window. A new and rapid process was developed to grow low frictional AgI coatings and a novel designed microstructure of nanoporous Ag filled with AgI (n-porous Ag/AgI) using a solution chemical method was also explored. The AgI coatings exhibited low friction coefficient and acceptable contact resistance. However, under very harsh conditions, their lifetime is too short. The initial tribotests showed high friction coefficient of the n-porous Ag/AgI coating, indicating an issue regarding its mechanical integrity. The use of graphene as a solid lubricant in sliding electrical contacts was investigated as well. The results show that graphene is an excellent solid lubricant in Ag-based contacts. Furthermore, the lubricating effect was found to be dependent on chemical composition of the counter surface. As an alternative lubricant, graphene oxide is cheaper and easier to produce. Preliminary tests with graphene oxide showed a similar frictional behavior as graphene suggesting a potential use of this material as lubricant in Ag contacts.

This thesis describes the development of a fast rate method for the deposition of high quality CdS and CdTe thin films. The technique uses Pulsed DC Magnetron Sputtering (PDCMS). Surprisingly, the technique produces highly stable process conditions. CREST is the first laboratory worldwide to show that pulsed DC power may be used to deposit CdS and CdTe thin films. This is a very promising process technology with potential for eventual industrial deployment. The major advantage is that the process produces high deposition rates suitable for use in solar module manufacturing. These rates are over an order of magnitude faster than those obtained by RF sputtering. In common with other applications it has also been found that the energetics of the pulsed DC process produce excellent thin film properties and the power supply configuration avoids the need for complex matching circuits. Conventional deposition methodologies for CdS, Chemical Bath Deposition (CBD) and CdTe thin films, Electrodeposition (ED), have been chosen as baselines to compare film properties with Pulsed DC Magnetron Sputtering (PDCMS). One of the issues encountered with the deposition of CdS thin films (window layers) was the presence of pinholes. A Plasma cleaning process of FTO-coated glass prior to the deposition of the CdS/CdTe solar cell has been developed. It strongly modifies and activates the TCO surface, and improves the density and compactness of the deposited CdS thin film. This, in turn, improves the optical and morphological properties of the deposited CdS thin films, resulting in a higher refractive index. The pinhole removal and the increased density allows the use of a much thinner CdS layer, and this reduces absorption of blue spectrum photons and thereby increases the photocurrent and the efficiency of the thin film CdTe cell. Replacing the conventional magnetic stirrer with an ultrasonic probe in the chemical bath (sonoCBD) was found to result in CdS films with higher optical density, higher refractive index, pinhole and void-free, more compact and uniform along the surface and through the thickness of the deposited material. PDCMS at 150 kHz, 500 W, 2.5 μs, 2 s, results in a highly stable process with no plasma arcing. It allows close control of film thickness using time only. The CdS films exhibited a high level of texture in the <001> direction. The grain size was typically ~50 nm. Pinholes and voids could be avoided by reducing the working gas pressure using gas flows ii below 20 sccm. The deposition rate was measured to be 1.33 nm/s on a rotating substrate holder. The equivalent deposition rate for a static substrate is 8.66 nm/s, which is high and much faster than can be achieved using a chemical bath deposition or RF magnetron sputtering. The transmission of CdS can be improved by engineering the band gap of the CdS layer. It has been shown that by adding oxygen to the working gas pressure in an RF sputtering deposition process it is possible to deposit an oxygenated CdS (CdS:O) layer with an improved band gap. In this thesis, oxygenated CdS films for CdTe TF-PV applications have been successfully deposited by using pulsed DC magnetron sputtering. The process is highly stable using a pulse frequency of 150 kHz and a 2.5 μs pulse reverse time. No plasma arcing was detected. A range of CdS:O films were deposited by using O2 flows from 1 sccm to 10 sccm during the deposition process. The deposition rates achieved using pulsed DC magnetron sputtering with only 500 W of power to the magnetron target were in the range ~1.49 nm/s ~2.44 nm/s, depending on the oxygen flow rate used. The properties of CdS thin films deposited by pulsed DC magnetron sputtering and chemical bath deposition have been studied and compared. The pulsed DC magnetron sputtering process produced CdS thin films with the preferred hexagonal <001> oriented crystalline structure with a columnar grain growth, while sonoCBD deposited films were polycrystalline with a cubic structure and small grainy crystallites throughout the thickness of the films. Examination of the PDCMS deposited CdS films confirmed the increased grain size, increased density, and higher crystallinity compared to the sonoCBD CdS films. The deposition rate for CdS obtained using pulsed DC magnetron sputtering was 2.86 nm/s using only 500 W power on a six inch circular target compared to the much slower (0.027 nm/s) for the sonoChemical bath deposited layers. CdTe thin films were grown on CdS films prepared by sonoCBD and Pulsed DC magnetron sputtering. The results showed that the deposition technique used for the CdS layer affected the growth and properties of the CdTe film and also determined the deposition rate of CdTe, being 3 times faster on the sputtered CdS. PDCMS CdTe layers were deposited at ambient temperature, 500 W, 2.9 μs, 10 s, 150 kHz, with a thickness of approximately 2 μm on CdS/TEC10 coated glass. The layers appear iii uniform and smooth with a grain size less than 100 nm, highly compact with the morphology dominated by columnar grain growth. Stress analysis was performed on the CdTe layers deposited at room temperature using different gas flows. Magnetron sputtered thin films deposited under low gas pressure are often subject to compressive stress due to the high mobility of the atoms during the deposition process. A possible way to reduce the stress in the film is the post-deposition annealing treatment. As the lattice parameter increased; the stress in the film is relieved. Also, a changing the deposition substrate temperature had an effect on the microstructure of CdTe thin films. Increasing the deposition temperature increased the grain size, up to ~600 nm. CdTe thin films with low stress have been deposited on CdS/TEC10 coated glass by setting the deposition substrate temperature at ~200°C and using high argon flows ~ 70 sccm Ar. Finally, broadband multilayer ARCs using alternate high and low refractive index dielectric thin films have been developed to improve the light transmission into solar cell devices by reducing the reflection of the glass in the extended wavelength range utilised by thin-film CdTe devices. A four-layer multilayer stack has been designed and tested, which operates across the wavelength range used by thin-film CdTe PV devices (400 850 nm). Optical modelling predicts that the MAR coating reduces the WAR (400-850 nm) from the glass surface from 4.22% down to 1.22%. The application of the MAR coating on a thin-film CdTe solar cell increased the efficiency from 10.55% to 10.93% or by 0.38% in absolute terms. This is a useful 3.6% relative increase in efficiency. The increased light transmission leads to improvement of the short-circuit current density produced by the cell by 0.65 mA/cm2. The MAR sputtering process developed in this work is capable of scaling to an industrial level.