Physical vapor deposition (PVD) refers to the removal of atoms from a solid or a liquid by physical means, followed by deposition of those atoms on a nearby surface to form a thin film or coating. Various approaches and techniques are applied to release the atoms including thermal evaporation, electron beam evaporation, ion-driven sputtering, laser ablation, and cathodic arc-based emission. Some of the approaches are based on a plasma discharge, while in other cases the atoms composing the vapor are ionized either due to the release of the film-forming species or they are ionized intentionally afterward. Here, a brief overview of the various PVD techniques is given, while the emphasis is on sputtering, which is dominated by magnetron sputtering, the most widely used technique for deposition of both metallic and compound thin films. The advantages and drawbacks of the various techniques are discussed and compared.

This thesis investigates lead oxides as photovoltaic materials. Vacuum deposition methods and ex-situ annealing are used to produce different stoichiometries of lead oxide. The relationship between structure and the optoelectronic properties is then investigated. Following this, a number of photovoltaic devices are prototyped and a Kelvin probe used to determine and understand the band structure of devices. Thin films of PbO produced via air annealing of thermally evaporated lead consist of a mixture of two phases, orthorhombic and tetragonal, that determine the materials properties and effectiveness as absorber layer in a Schottky device. Films of higher tetragonal content are more photoactive, showing lower series resistance. Kelvin probe reveals that with an increasing work function of the PbO with increasing duration of the annealing, the Schottky barrier between PbO and Al increases, which results in a higher VOC. This trend is inverted when the Fermi level of PbO drops below that of ITO, creating an opposing junction. Reactively sputtered PbO2 films are highly conductive degenerate semiconductors. Increasing oxygen flow rate during deposition leads to increased resistivity and decreased mobility, resulting from a decrease in grain size. Alongside this an increase in carrier concentration is observed as the material gets less ordered at higher oxygen flow rates, which results in an increase in Fermi level. Due to its high conductivity the material is not photoactive, and the high work function between -5.6 and -5.8 eV does not allow the formation of a Schottky junction or a p-n junction with the evaporated p- type PbO. Post deposition annealing of the sputtered films leads to the formation of the more resistive Pb3O4 phase. This material shows lower carrier concentration and mobility, however, work functions are similarly high. The changes induced by the heat treatment are not substantial enough to be able to create a junction between the as-deposited and the annealed material, as is revealed by Kelvin probe and Hall Effect measurements. Heterojunctions between P3HT and Pb3O4 were made to test predictions made by KP measurements. A heat treatment on P3HT improved its electronic properties and raised the Fermi level, resulting in the transformation of a diode in to a photovoltaic device and a decrease in dark current.

<p>Ferroelectrics are a group of advanced electronic materialswith a wide variety of properties useful in applications suchas memory devices, resonators and filters, infrared sensors,microelectromechanical systems, and optical waveguides andmodulators. Among the oxide perovskite-structured ferroelectricthin film materials sodium potassium niobate or Na0.5K0.5NbO3(NKN) has recently emerged as one of the most promisingmaterials in microwave applications due to high dielectrictunability and low dielectric loss. This licentiate thesispresents results on growth and structural, optical, andelectrical characterization of Na0.5K0.5NbO3 thin films. Thefilms were deposited by rf-magnetron sputtering of astoichiometric, high density, ceramic Na0.5K0.5NbO3 target ontosingle crystal LaAlO3 and Al2O3, and polycrystalline Pt80Ir20substrates. By x-ray diffractometry, NKN films on c-axisoriented LaAlO3 substrates were found to grow epitaxially,whereas films on hexagonal sapphire and polycrystallinePt80Ir20 substrates were found to be preferentially (00l)oriented. Optical and waveguiding properties of theNa0.5K0.5NbO3/Al2O3 heterostructure were characterized using aprism-coupling technique. Sharp and distinguishable transversemagnetic (TM) and electric (TE) propagation modes wereobserved. The extraordinary and ordinary refractive indiceswere calculated to ne = 2.216±0.003 and no =2.247±0.002 for a 2.0 μm thick film at λ = 632.8nm. This implies a birefringence Δn = ne - no =-0.031±0.003 in the film. The ferroelectric state inNKN/Pt80Ir20 films at room temperature was indicated by apolarization loop with polarization as high as 33.4 μC/cm2at 700 kV/cm, remnant polarization of 9.9 μC/cm2 andcoercive field of 91 kV/cm. Current-voltage characteristics ofvertical Au/NKN/Pt80Ir20 capacitive cells and planar Au/NKN/LaAlO3 interdigital capacitors (IDCs) showed very goodinsulating properties, with the leakage current density for anNKN IDC on the order of 30 nA/cm2 at 400 kV/cm. Rf dielectricspectroscopy demonstrated low loss, low frequency dispersion,and high voltage tunability. At 1 MHz NKN/LaAlO3 showed adissipation factor tan δ of 0.010 and a tunability of 16.5% at 200 kV/cm. For the same structure the frequencydispersion, Δεr, between 1 kHz and 1 MHz was 8.5%.</p><p><b>Key words:</b>ferroelectrics, sodium potassium niobates,thin films, rf-magnetron sputtering, waveguiding, refractiveindex, prism coupling, dielectric tunability</p>

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The present thesis addresses two research areas related to film growth in a highly ionized magnetron sputtering system: plasma characterization, and thin film growth and analysis. The deposition technique used is called high power pulsed magnetron sputtering (HPPMS). Characteristic for this technique are high energy pulses (a few Joules) of length 50-100 µs that are applied to the target (cathode) with a duty time of less than 1 % of the total pulse time. This results in a high electron density in the discharge (&gt;1x1019 m-3) and leads to an increase of the ionization fraction of the sputtered material reaching up to 70 % for Cu. In this work the spatial and temporal evolution of the plasma parameters, including the electron energy distribution function (EEDF), the electron density and the electron temperature are determined using electrostatic Langmuir probes. Electron temperature measurements reveal a low effective temperature of 2-3 eV. The degree of ionization in the HPPMS discharge is explained in light of the self-sputtering yield of the target material. A simple model is therefore provided in order to compare the sputtering yield in HPPMS and that in dc magnetron sputtering (dcMS) for the same average power. Thin Ta films are grown using HPPMS and dcMS and their properties are studied. It is shown that enhanced microstructure and morphology of the deposited films is achieved by HPPMS. The Ta films are also deposited at a number of substrate inclination angles ranging from 0o (i.e., facing the target surface) up to 180 o (i.e., facing away from the target). Deposition rate measurements performed at all inclination angles for both techniques, reveal that growth made using HPPMS resulted in an improved film thickness at higher inclination. Furthermore, the high ionization of the Ta atoms in HPPMS discharge is found to allow for phase tailoring of the deposited films at all inclination angles by applying a bias voltage to the substrate. Finally, highly ionized magnetron sputtering of a compound MAX-phase material (Ti3SiC2) is performed, demonstrating that the HPPMS discharge could also be used to tailor the composition of the growing Ti-Si-C films. / On the day of the public defence of the doctoral thesis, the status of articles III and IV was Submitted. The titles of papers VI and VII changed between their manuscript forms and when they were published.

In plasma assisted thin film growth, control over the energy and direction of the incoming species is desired. If the growth species are ionized this can be achieved by the use of a substrate bias or a magnetic field. Ions may be accelerated by an applied potential, whereas neutral particles may not. Thin films grown by ionized physical vapor deposition (I-PVD) have lately shown promising results regarding film structure and adhesion. High power impulse magnetron sputtering (HIPIMS) is a relatively newly developed technique, which relies on the creation of a dense plasma in front of the sputtering target to produce a large fraction of ions of the sputtered material. In HIPIMS, high power pulses with a length of ~100 μs are applied to a conventional planar magnetron. The highly energetic nature of the discharge, which involves power densities of several kW/cm2, creates a dense plasma in front of the target, which allows for a large fraction of the sputtered material to be ionized. The work presented in this thesis involves plasma analysis using electrostatic probes, optical emission spectroscopy (OES), magnetic probes, energy resolved mass spectrometry, and other fundamental observation techniques. These techniques used together are powerful plasma analysis tools, and used together give a good overview of the plasma properties is achieved. from the erosion zone of the magnetron. The peak plasma density during the active cycle of the discharge exceeds 1019 electrons/m3. The expanding plasma is reflected by the chamber wall back into the center part of the chamber, resulting in a second density peak several hundreds of μs after the pulse is turned off. Optical emission spectroscopy (OES) measurements of the plasma indicate that the degree of ionization of sputtered Ti is very high, over 90 % in the peak of the pulse. Even at relatively low applied target power (~200 W/cm2 peak power) the recorded spectrum is totally dominated by radiation from ions. The recorded HIPIMS spectra were compared to a spectrum taken from a DC magnetron discharge, showing a completely different appearance. Magnetic field measurements performed with a coil type probe show significant deformation in the magnetic field of the magnetrons during the pulse. Spatially resolved measurements show evidence of a dense azimuthally E×B drifting current. Circulating currents mainly flow within 2 away cm from the target surface in an early part of the pulse, to later diffuse axially into the chamber and decrease in intensity. We record peak current densities of the E×B drift to be of the order of 105 A/m2. A mass spectrometry (MS) study of the plasma reveals that the HIPIMS discharge contains a larger fraction of highly energetic ions as compared to the continuous DC discharge. Especially ions of the target material are more energetic. Time resolved studies show broad distributions of ion energies in the early stage of the discharge, which quickly narrows down after pulse switch-off. Ti ions with energies up to 100 eV are detected. The time average plasma contains mainly low energy Ar ions, but during the active phase of the discharge, the plasma is highly metallic. Shortly after pulse switch-on, the peak value of the Ti1+/Ar1+ ratio is over 2. The HIPIMS discharge also contains a significant amount of doubly charged ions.

The goal of this research was to devise a new analytical technique, using Accelerator Mass Spectrometry (AMS), to measure Platinum Group Element (PGE) concentrations to the sup-ppb levels in natural, insulating, samples. The challenges were threefold. First, a method of sputtering an insulating sample to successfully produce a stable beam of anions needed to be devised. Second, a suitable standard of known PGE concentrations had to be found and third, spectral analysis of the beam had to verify any claims of PGE abundance. The first challenge was met by employing a modified high intensity negative ion source flooded with neutral caesium that successfully sputtered insulators to produce a beam of negative ions. The second challenge, that of finding a suitable standard, was fraught with difficulties, as no synthesized standards available were found to be appropriate for this work. As a result, direction is provided for future production of standards by ion implantation. The third challenge, successful spectral analysis, was accomplished using a newly designed gas ionization detector which allowed for resolution of the interfering molecular fragment from the PGE ions. Coupled with the use of the SRIM computer programme, positive identification of all peaks in the spectra of the analyzed samples was accomplished. The success of the first and third challenges lead to the qualitative analyses of geological samples for sub-ppb levels of PGE by AMS. Quantitative analyses await only for the appropriate standards and with those will come a whole new range of research possibilities for measuring sub-ppb levels of PGE in insulating samples by AMS.

Transparent oxide semiconducting films have continued to receive considerable attention, from a fundamental and application-based point of view, primarily because of their useful fundamental properties. Of particular interest is zinc oxide (ZnO), an n-type semiconductor that exhibits excellent optical, electrical, catalytic and gas-sensing properties, and has many applications in various fields. In this work, thin film transistor (TFT) arrays based on ZnO have been prepared by reactive radio frequency (RF) magnetron sputtering. Prior to the TFT fabrication, ZnO layers were sputtered on to glass and silicon substrates, and the deposition parameters optimised for electrical resistivities suitable for TFT applications. The sputtering process was carried out at room temperature with no intentional heating. The aim of this work is to prepare ZnO thin films with stable semiconducting electrical properties to be used as the active channel in TFTs; and to understand the role of intrinsic point defects in device performance and stability. The effect of oxygen (O2) adsorption on TFT device characteristics is also investigated. The structural quality of the material (defect type and concentration), electrical and optical properties (transmission/absorption) of semiconductor materials are usually closely correlated. Using the Vienna ab-initio simulation package (VASP), it is predicted that O2 adsorption may influence film transport properties only within a few atomic layers beneath the adsorption site. These findings were exploited to deposit thin films that are relatively stable in atmospheric ambient with improved TFT applications. TFTs incorporating the optimised layer were fabricated and demonstrated very impressive performance metrics, with effective channel mobilities as high as 30 cm2/V-1s-1, on-off current ratios of 107 and sub-threshold slopes of 0.9 – 3.2 V/dec. These were found to be dependent on film thickness (~15 – 60 nm) and the underlying dielectric (silicon dioxide (SiO2), gadolinium oxide (Gd2O3), yttrium oxide (Y2O3) and hafnium oxide (HfO2)). In this work, prior to sputtering the ZnO layer (using a ZnO target of 99.999 % purity), the sputtering chamber was evacuated to a base pressure ~4 x 10-6 Torr. Oxygen (O2) and argon (Ar) gas (with O2/Ar ratio of varying proportions) were then pumped into the chamber and the deposition process optimised by varying the RF power between 25 and 500 W and the O2/Ar ratio between 0.010 to 0.375. A two-level factorial design technique was implemented to test specific parameter combinations (i.e. RF power and O2/Ar ratio) and then statistical analysis was utilised to map out the responses. The ZnO films were sputtered on glass and silicon substrates for transparency and resistivity measurements, and TFT fabrication respectively. For TFT device fabrication, ZnO films were deposited onto thermally-grown silicon dioxide (SiO2) or a high-k dielectric layer (HfO2, Gd2O3 and Y2O3) deposited by a metal-organic chemical deposition (MOCVD) process. Also, by using ab initio simulation as implemented in the “Vienna ab initio simulation package (VASP)”, the role of oxygen adsorption on the electrical stability of ZnO thin film is also investigated. The results indicate that O2 adsorption on ZnO layers could modify both the electronic density of states in the vicinity of the Fermi level and the band gap of the film. This study is complemented by studying the effects of low temperature annealing in air on the properties of ZnO films. It is speculated that O2 adsorption/desorption at low temperatures (150 – 350 0C) induces variations in the electrical resistance, band gap and Urbach energy of the film, consistent with the trends predicted from DFT results.