In this work, small signal DC voltage dependent dielectric permittivity, loss tangent, and tuneability of magnetron sputtered epitaxial Na0.5K0.5NO3 films are studied experimentally. (100)-oriented Na0.5K0.5NbO3 films are deposited onto SiO2-buffered CMOS grade low resistivity (p = 10-20 cm) and high resistivity (p = 15-45 kcm) silicon substrates. Planar capacitors with 2 or 4 m gaps between electrodes have been fabricated on top of ferroelectric films. These devices have been characterized in the frequency range 1.0 MHz to 50 GHz at temperatures 30 - 300K. Na0.5K0.5NbO3/SiO2/Si structures on high resistivity silicon substrate exhibit C-V performances typical for Metal-Insulator- Semiconductor (MIS) capacitors. At low frequencies, f 1.0 GHz, the large tuneability and large losses are associated with the MIS structure, while at higher microwave frequencies the tuneability is mainly associated with the ferroelectric, film. At 1.0 MHz and room temperature, the tuneability of Na0.5K0.5NbO3/SiO2/Si structures more than 90%, reducing to 10-15 % at 50 GHz. The losses decrease with increasing the DC bias and frequency. A Q-factor more than 15 at 50 GHz is observed. The dielectric permittivity of the Na0.5K0.5NbO3 film is in the range 50-150 at frequencies 0.045-50 GHz. On low resistivity substrate the performance of Na0.5K0.5NbO3 films is completely screened by the high losses in silicon, and the tuneability is negligible. © 2001 Taylor and Francis.

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The work presented in this thesis deals with reactive magnetron sputtering processes of metal oxides with a prime focus on high power impulse magnetron sputtering (HiPIMS). The aim of the research is to contribute towards understanding of the fundamental mechanisms governing a reactive HiPIMS process and to investigate their implications on the film growth.

The stabilization of the HiPIMS process at the transition zone between the metal and compound modes of Al-O and Ce-O was investigated for realizing the film deposition with improved properties and higher depositionrate and the results are compared with direct current magnetron sputtering (DCMS) processes. The investigations were made for different sputtering conditions obtained by varying pulse frequency, peak power and pumping speed. For the experimental conditions employed, it was found that reactive HiPIMS can eliminate/suppress the hysteresis effect for a range of frequency, leading to a stable deposition process with a high deposition rate. The hysteresis was found to be eliminated for Al-O while for Ce-O, it was not eliminated but suppressed as compared to the DCMS. The behavior of elimination/suppression of the hysteresis may be influenced by high erosion rate during the pulse, limited target oxidation between the pulses and gas rarefaction effects in front of the target. Similar investigations were made for Ti-O employing a larger target and the hysteresis was found to be suppressed as compared to the respective DCMS, but not eliminated. It was shown that the effect of gas rarefaction is a powerful mechanism for preventing oxide formation upon the target surface. The impact of this effect depends on the off-time between the pulses. Longer off-times reduce the influence of gas rarefaction.

To gain a better understanding of the discharge current-voltage behavior in a reactive HiPIMS process of metal oxides, the ion compositions and ion energy distributions were measured for Al-O and Ti-O using time averaged and time-resolved mass spectrometry. It was shown that the different discharge current behavior between non-reactive and reactive modes couldn’t be explained solely by the change in the secondary electron emission yield from the sputtering target. The high fluxes of O¹⁺ ions contribute substantially to the discharge current giving rise to an increase in the discharge current in the oxide mode as compared to the metal mode. The results also show that the source of oxygen in the discharge is both, the target surface (via sputtering) as well as the gas phase.

The investigations on the properties of HiPIMS grown films were made by synthesizing metal oxide thin films using Al-O, Ti-O and Ag-Cu-O. It was shown that Al₂O₃ films grown under optimum condition using reactive HiPIMS exhibit superior properties as compared to DCMS. The HiPIMS grown films exhibit higher refractive index as well as the deposition rate of the film growth was higher under the same operating conditions. The effect of HiPIMS peak power on TiO₂ film properties was investigated and the results are compared with the DCMS. The properties of TiO₂ films such as refractive index, film density and phase structure were experimentally determined. The ion composition during film growth was investigated and an explanation on the correlation of the film properties and ion energy was made. It was found that energetic and ionized sputtered flux in reactive HiPIMS can be used to tailor the phase formation of the TiO₂ films with high peak powers facilitating the rutile phase while the anatase phase can be obtained using low peak powers. These phases can be obtained at room temperature without external substrate heating or post-deposition annealing which is in contrast to the reactive DCMS where both, anatase and rutile phases of TiO₂ are obtained at either elevated growth temperatures or by employing post deposition annealing. The effect of HiPIMS peak power on the crystal structure of the grown films was also investigated for ternary compound, Ag-Cu-O, for which films were synthesized using reactive HiPIMS as well as reactive DCMS. It was found that the stoichiometric Ag₂Cu₂O₃ can be synthesized by all examined pulsing peak powers. The oxygen gas flow rate required to form stoichiometric films is proportional to the pulsing peak power in HiPIMS. DCMS required low oxygen gas flow to synthesis the stoichiometric films. The HiPIMS grown films exhibit more pronounced crystalline structure as compared to the films grown using DCMS. This is likely an effect of highly ionized depositing flux which facilitates an intense ion bombardment during the film growth using HiPIMS. Our results indicate that Ag₂Cu₂O₃film formation is very sensitive to the ion bombardment on the substrate as well as to the backattraction of metal and oxygen ions to the target.

The discharge current behavior in reactive high power impulse magnetron sputtering (HiPIMS) of Ti-O and Al-O is investigated. It is found that for both metals, the discharge peak current significantly increases in the oxide mode in contrast to the behavior in reactive direct current magnetron sputtering where the discharge current increases for Al but decreases for Ti when oxygen is introduced. In order to investigate the increase in the discharge current in HiPIMS-mode, the ionic contribution of the discharge in the oxide and metal mode is measured using time-resolved mass spectrometry. The energy distributions and time evolution are investigated during the pulse-on time as well as in the post-discharge. In the oxide mode, the discharge is dominated by ionized oxygen, which has been preferentially sputtered from the target surface. The ionized oxygen determines the discharge behavior in reactive HiPIMS.

The effect of peak power in a high power impulse magnetron sputtering (HiPIMS) reactive deposition of TiO(2) films has been studied with respect to the deposition rate and coating properties. With increasing peak power not only the ionization of the sputtered material increases but also their energy. In order to correlate the variation in the ion energy distributions with the film properties, the phase composition, density and optical properties of the films grown with different HiPIMS-parameters have been investigated and compared to a film grown using direct current magnetron sputtering (DCMS). All experiments were performed for constant average power and pulse on time (100W and 35 mu s, respectively), different peak powers were achieved by varying the frequency of pulsing. Ion energy distributions for Ti and O and its dependence on the process conditions have been studied. It was found that films with the highest density and highest refractive index were grown under moderate HiPIMS conditions (moderate peak powers) resulting in only a small loss in mass-deposition rate compared to DCMS. It was further found that TiO2 films with anatase and rutile phases can be grown at room temperature without substrate heating and without post-deposition annealing.

In the further development of reactive sputter deposition, strategies which allow for stabilization of the transition zone between the metallic and compound modes, elimination of the process hysteresis, and increase of the deposition rate, are of particular interest. In this study, the hysteresis behavior and the characteristics of the transition zone during reactive high power impulse magnetron sputtering (HiPIMS) of Al and Ce targets in an Ar-O(2) atmosphere as a function of the pulsing frequency and the pumping speed are investigated. Comparison with reactive direct current magnetron sputtering (DCMS) reveals that HiPIMS allows for elimination/suppression of the hysteresis and a smoother transition from the metallic to the compound sputtering mode. For the experimental conditions employed in the present study, optimum behavior with respect to the hysteresis width is obtained at frequency values between 2 and 4 kHz, while HiPIMS processes with values below or above this range resemble the DCMS behavior. Al-O films are deposited using both HiPIMS and DCMS. Analysis of the film properties shows that elimination/suppression of the hysteresis in HiPIMS facilitates the growth of stoichiometric and transparent Al(2)O(3) at relatively high deposition rates over a wider range of experimental conditions as compared to DCMS.

Ag₂Cu₂O₃ thin films were prepared by reactive high power impulse magnetron sputtering (HiPIMS) from an alloy silver-copper (Ag0.5Cu0.5) target on silicon and glass substrates. The effects of the oxygen gas flow and the peak power on the structural properties of the films were investigated. Structural characterization by grazing incidence X-ray diffraction measurements show that the structure of Ag₂Cu₂O₃ is related to the oxygen flow and the peak power. Films grown with high peak power required higher oxygen flow rate in order to get stoichiometric Ag₂Cu₂O₃ thin films. It was further found that using HiPIMS, polycrystalline Ag₂Cu₂O₃ films can be grown at room temperature without substrate heating or post-deposition annealing, while films deposited by DCMS exhibit poor crystallinity under the same process conditions.

Poster

In this research, high power impulse magnetron sputtering (HiPIMS) based new deposition processes are introduced to address; the issue of low degree of ionization of C in magnetron sputtering discharges, and the difficulty encountered in thin film deposition on complex-shaped surfaces. The issue of low degree of C ionization is addressed by introducing a new strategy which is based on promoting the electron impact ionization ofC by increasing the electron temperature in the plasma discharge using Ne, instead of conventionally used Ar. The Ne-based HiPIMS process provides highly ionized C fluxes which are essential for the synthesis of high-density and sp³ rich amorphous carbon (a-C) thin films such as diamond-like carbon (DLC) and tetrahedral a-C (ta-C). The feasibility of coating complex-shaped surfaces is demonstrated by using the dual-magnetron approach in an open-field (magnetic field of the magnetrons) configuration and performing sideways deposition of Ti films. The HiPIMS-based open-field configuration process enhances the sideways transport of the sputtered flux — an effect which is observed in the case of HiPIMS.

The characterization of the Ne-HiPIMS discharge using a Langmuir probe and mass spectrometry shows that it provides an increase in the electron temperature resulting in an order of magnitude decrease in the mean ionization length of the sputtered C as compared to the conventional Ar-HiPIMS discharge. The C1+ ion energy distribution functions exhibit the presence of an energetic C¹⁺ ion population and a substantial increase in the total C¹⁺ ion flux. The higher C¹⁺ ion flux facilitates the growth of sp³ rich carbon films with mass densities, measured by x-ray reflectometry, reaching as high as approx. 2.8 gcm^-3.

The dual-magnetron open-field configuration process is operated in DCMS as well as in HiPIMS modes. The plasma characterization, performed by Langmuir probe measurements and optical emission spectroscopy, shows that the plasma density in the Ti-HiPIMS discharge is higher than that of the Ti-DCMS discharge. This results in the higher ionized fraction of the sputtered Ti in the case of HiPIMS. The film uniformity and the deposition rate of the film growth, obtained by employing scanning electron microscopy, demonstrate that the sideways deposition approach can be used for depositing thin films on complex-shaped surfaces.

The work presented in this thesis deals with synthesis of carbon-based as well as metal-oxide thin films using highly ionized plasmas. The principal deposition method employed was high power impulse magnetron sputtering (HiPIMS). The investigations on plasma chemistry, plasma energetics, plasma-film interactions and its correlation to film growth and resulting film properties were made. The thesis is divided into two parts: (i) HiPIMS-based deposition of carbon-based thin films and (ii) HiPIMS-based deposition of metal-oxide thin films.

In the first part of the thesis, HiPIMS based strategies are presented that were developed to address the fundamental issues of low degree of carbon ionization and low deposition rates of carbon film growth in magnetron sputtering. In the first study, a new strategy was introduced for increasing the degree of ionization of sputtered carbon via increasing the electron temperature in the discharge by using a higher ionization potential buffer gas (Ne) in place of commonly used Ar. A direct consequence of enhanced electron temperatures was observed in the form of measured large fluxes of ionized carbon at the substrate position. Consequently, high mass densities of the resulting amorphous carbon (a-C) thin films reaching 2.8 g/cm³ were obtained.

In another study, feasibility of HiPIMS-based high density discharges for high-rate synthesis of dense and hard a-C thin films was explored. A strategy was compiled and implemented that entailed coupling a hydrocarbon precursor gas (C₂H₂) with high density discharges generated by the superposition of HiPIMS and direct current magnetron sputtering (DCMS). Appropriate control of discharge density (by tuning HiPIMS/DCMS power ratio), gas phase composition and energy of the ionized depositing species lead to a route capable of providing ten-fold increase in the deposition rate of a-C film growth compared to that obtained using HiPIMS Ar discharge in the first study. The increased deposition rate was achieved without significant incorporation of H (<10 %) and with relatively high hardness (>25 GPa) and mass density (~2.32 g/cm³). The knowledge gained in this work was utilized in a subsequent work where the feasibility of adding high ionization potential buffer gas (Ne) to increase the electron temperature in an Ar/C₂H₂ HiPIMS discharge was explored. It was found that the increased electron temperature lead to enhanced dissociation of hydrocarbon precursor and an increased H incorporation into the growing film. The resulting a-C thin films exhibited high hardness (~ 25 GPa), mass densities in the order of 2.2 g/cm³ and H content as low as about 11%. The striking feature of the resulting films was low stress levels where the films exhibited compressive stresses in the order of 100 MPa.

In the second part of the thesis, investigations on reactive HiPIMS discharge characteristics were made for technologically relevant metal-oxide systems. In the first study, the discharge characteristics of Ti-O and Al-O were investigated by studying the discharge current characteristics and measuring the ion flux composition. Both, Ti-O and Al-O discharges were dominated by large fluxes of ionized metallic as well as sputtering and reactive gases species. The generation of large ionized fluxes influenced the discharge characteristics consequently surpassing the changes in the secondary electron emission yields which, in the case of DCMS discharges entail contrasting behavior of the discharge voltage for the two material systems. The study also suggested that the source of oxygen ions in the case of reactive HiPIMS is both, the target surface (via sputtering) as well as gas phase.

In a subsequent study, the knowledge gained from the studies on metal-oxide HiPIMS discharges was utilized for investigating the behavior of reactive HiPIMS discharges related to ternary compound thin film growth. In this work Al-Si-O system, which is a promising candidate for anti-reflective and solar thermal applications, was employed to carry out the investigations under varied target compositions (Al, Al0.5Si0.5, and Al0.1Si0.9). It was found that the discharge current behavior of metal and oxide modes of Al-Si-O HiPIMS discharges were similar to those of Al-O and were independent of the target composition. The influence of energy and composition of the ionized depositing fluxes on the film growth was also investigated. It was shown that stoichiometric Al-Si-O thin films exhibiting a refractive index below 1.6 (which is desired for anti-reflective applications) can be grown. Furthermore, the refractive index and chemical composition of the resulting films were found to be unchanged with respect to the energy of the depositing species.

The effect of ionized deposition fluxes that are generated in metal-oxide HiPIMS discharges was also investigated for the phase composition and optical properties of TiO2 thin films. It was found that energetic and ionized sputtered flux in reactive HiPIMS can be used to tailor the phase formation of the TiO2 films with high peak powers facilitating the rutile phase while the anatase phase can be obtained using low peak powers. It was also demonstrated that using HiPIMS, these phases can be obtained at room temperature without external substrate heating or  post-deposition annealing. The results on plasma and film properties were also compared with DCMS.

Broad band anti-reflective multilayer coatings require the use of a low-index material as a top layer. Normally SiO₂ is used which exhibits sufficiently low refractive index (~1.5 at 550 nm) yet its low hardness (~10 GPa) hinders its application in abrasive environments. A strategy to circumnavigate these limitations is the synthesis of multicomponent materials that combine good mechanical and optical performance. In this work we synthesize Al-Si-O thin films seeking to combine the low refractive index of SiO₂ and the relatively high hardness of Al₂O₃. The potential of reactive high power impulse magnetron sputtering (HiPIMS) for synthesizing Al-Si-O suitable for top-layers in anti-reflective coating stacks is explored by depositing films in an Ar⁺O₂ ambient under varied target compositions (Al_0.5Si_0.5 and Al_0.1Si_0.9). The behavior of discharge current in metal and oxide mode is correlated with the plasma composition, plasma energetics as well as target surface composition in order to obtain information about the chemical nature and the energy of the film forming species. Plasma composition and plasma energetics are investigated by measuring electron density, electron temperature as well as energy distributions and as fluxes of Ar⁺, Al⁺, Si⁺ and O+ ions. Monte-Carlo based computer simulations are employed to assess the ion-target surface interactions to gain insight into the discharge characteristics as well as film growth. The properties of the grown films (chemical composition, mechanical and optical properties) are investigated and an understanding of the reactive HiPIMS-based growth of anti-reflective Al-Si-O thin films is established. For reference, the plasma and film properties of Al-O are also studied.

Amorphous carbon (a-C) thin films are synthesized using high power impulse magnetron sputtering (HiPIMS) based Ne-Ar/C₂H₂ discharges. Plasma properties and film growth are investigated under different gas phase composition and operating pressures. Film mass densities, H content, hardness and compressive stresses are measured. Mass densities in the order of 2.2 g/cm³, hardness close to 25 GPa and H content as low as 11% are obtained. The film properties manifest a dependence on energy and flux of the depositing species and energetic ion bombardment driven structural changes in the films are found to govern the resulting film properties.

Hydrogenated diamondlike carbon (DLC:H) thin films exhibit many interesting properties that can be tailored by controlling the composition and energy of the vapor fluxes used for their synthesis. This control can be facilitated by high electron density and/or high electron temperature plasmas that allow one to effectively tune the gas and surface chemistry during film growth, as well as the degree of ionization of the film forming species. The authors have recently demonstrated by adding Ne in an Ar-C high power impulse magnetron sputtering (HiPIMS) discharge that electron temperatures can be effectively increased to substantially ionize C species [Aijaz et al., Diamond Relat. Mater. 23, 1 (2012)]. The authors also developed an Ar-C2H2 HiPIMS process in which the high electron densities provided by the HiPIMS operation mode enhance gas phase dissociation reactions enabling control of the plasma and growth chemistry [Aijaz et al., Diamond Relat. Mater. 44, 117 (2014)]. Seeking to further enhance electron temperature and thereby promote electron impact induced interactions, control plasma chemical reaction pathways, and tune the resulting film properties, in this work, the authors synthesize DLC: H thin films by admixing Ne in a HiPIMS based Ar/C2H2 discharge. The authors investigate the plasma properties and discharge characteristics by measuring electron energy distributions as well as by studying discharge current characteristics showing an electron temperature enhancement in C2H2 based discharges and the role of ionic contribution to the film growth. These discharge conditions allow for the growth of thick (amp;gt;1 mu m) DLC: H thin films exhibiting low compressive stresses (similar to 0.5 GPa), high hardness (similar to 25 GPa), low H content (similar to 11%), and density in the order of 2.2 g/cm(3). The authors also show that film densification and change of mechanical properties are related to H removal by ion bombardment rather than subplantation. (C) 2016 American Vacuum Society.

A dual-magnetron system for deposition inside tubular substrates has been developed. The two magnetrons are facing each other and have opposing magnetic fields forcing electrons and thereby also ionized material to be transported radially towards the substrate. The depositions were made employing direct current magnetron sputtering (DCMS) and high power impulse magnetron sputtering (HiPIMS). To optimize the deposition rate, the system was characterized at different separation distances between the magnetrons under the same sputtering conditions. The deposition rate is found to increase with increasing separation distance independent of discharge technique. The emission spectrum from the HiPIMS plasma shows a highly ionized fraction of the sputtered material. The electron densities of the order of 10(16) m(-3) and 10(18) m(-3) have been determined in the DCMS and the HiPIMS plasma discharges respectively. The results demonstrate a successful implementation of the concept of sideways deposition of thin films providing a solution for coating complex shaped surfaces.

A strategy that facilitates a substantial increase of carbon ionization in magnetron sputtering discharges is presented in this work. The strategy is based on increasing the electron temperature in a high power impulse magnetron sputtering discharge by using Ne as the sputtering gas. This allows for the generation of an energetic C⁺ ion population and a substantial increase in the C⁺ ion flux as compared to a conventional Ar-HiPIMS process. A direct consequence of the ionization enhancement is demonstrated by an increase in the mass density of the grown films up to 2.8 g/cm³; the density values achieved are substantially higher than those obtained from conventional magnetron sputtering methods.

In the present study we contribute to the understanding that is required for designing sputtering-based routes for high rate synthesis of hard and dense amorphous carbon (a-C) films. We compile and implement a strategy for synthesis of a-C thin films that entails coupling a hydrocarbon gas (acetylene) with high density discharges generated by the superposition of high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS). Appropriate control of discharge density (by tuning HiPIMS/DCMS power ratio), gas phase composition and energy of the ionized depositing species leads to a route capable of providing ten-fold increase in the deposition rate of a-C film growth compared to HiPIMS Ar discharge (Aijaz et al. Diamond and Related Materials 23 (2012) 1). This is achieved without significant incorporation of H (< 10 %) and with relatively high hardness (> 25 GPa) and mass density (~2.32 g/cm³). Using our experimental data together with Monte-Carlo computer simulations and data from the literature we suggest that: (i) dissociative reactions triggered by the interactions of energetic discharge electrons with hydrocarbon gas molecules is an important additional (to the sputtering cathode) source of film forming species and (ii) film microstructure and film hydrogen content are primarily controlled by interactions of energetic plasma species with surface and sub-surface layers of the growing film.

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 (>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.

Ta thin films were grown on Si substrates at different inclination angles with respect to the sputter source using high power impulse magnetron sputtering (HIPIMS), an ionized physical vapor deposition technique. The ionization allowed for better control of the energy and directionality of the sputtered species, and consequently for improved properties of the deposited films. Depositions were made on Si substrates with the native oxide intact. The structure of the as deposited films was investigated using X-ray diffraction, while a four-point probe setup was used to measure the resistivity. A substrate bias process-window for growth of bcc-Ta was observed. However, the process-window position changed with changing inclination angles of the substrate. The formation of this low-resistivity bcc-phase could be understood in light of the high ion flux from the HIPIMS discharge.

We have deposited Ti-Si-C thin films using high-power impulse magnetron sputtering (HIPIMS) from a Ti₃SiC₂ compound target. The as-deposited films were composite materials with TiC as the main crystalline constituent. X-ray diffraction and photoelectron spectroscopy indicated that they also contained amorphous SiC, and for films deposited on inclined substrates, crystalline Ti₅Si₃C_x. The film morphology was dense and flat, while films deposited with dc magnetron sputtering under comparable conditions were rough and porous. Due to the high degree of ionization of the sputtered species obtained in HIPIMS, it is possible to control the film composition, in particular the C content, by tuning the substrate inclination angle, the Ar process pressure, and the bias voltage.

We report on electrostatic probe measurements of a high-power pulsed magnetron discharge. Space- and time-dependent characteristics of the plasma parameters are obtained as functions of the process parameters. By applying high-power pulses (peak power of ~0.5 MW), with a pulse-on time of ~100 µs and a repetition frequency of 20 ms, peak electron densities of the order of ~10¹⁹ m^{− 3}, i.e. three orders of magnitude higher than for a conventional dc magnetron discharge, are achieved soon after the pulse is switched on. At high sputtering gas pressures (>5 mTorr), a second peak occurs in the electron density curve, hundreds of microseconds after the pulse is switched off. This second peak is mainly due to an ion acoustic wave in the plasma, reflecting off the chamber walls. This is concluded from the time delay between the two peaks in the electron and ion saturation currents, which is shown to be dependent on the chamber dimensions and the sputtering gas composition. Finally, the electron temperature is determined, initially very high but decreasing rapidly as the pulse is turned off. The reduction seen in the electron temperature, close to the etched area of the cathode, is due to cooling by the sputtered metal atoms.

We have synthesized Ta thin films on Si substrates placed along a wall of a 2-cm-deep and 1-cm-wide trench, using both a mostly neutral Ta flux by conventional dc magnetron sputtering (dcMS) and a mostly ionized Ta flux by high-power pulsed magnetron sputtering (HPPMS). Structure of the grown films was evaluated by scanning electron microscopy, transmission electron microscopy, and atomic force microscopy. The Ta thin film grown by HPPMS has a smooth surface and a dense crystalline structure with grains oriented perpendicular to the substrate surface, whereas the film grown by dcMS exhibits a rough surface, pores between the grains, and an inclined columnar structure. The improved homogeneity achieved by HPPMS is a direct consequence of the high ion fraction of sputtered species.

Radio frequency sputtering has been used to deposit -alumina (-Al₂O₃) thin films at substrate temperatures of 280–560 °C. The films are shown to be single phased and hard. Nanoindentation gives values of 306±31 and 27±3 GPa for elastic modulus and hardness, respectively, for a substrate temperature of 280 °C. Growth of the phase was achieved by in situ predeposition of a chromia template layer. Chromia crystallizes in the same hexagonal structure as -alumina, with a lattice mismatch of 4.1% in the a- and 4.6% in the c-parameter, and is shown to nucleate readily on the amorphous substrates (silicon with a natural oxide layer). This results in local epitaxy of -alumina on the chromia layer, as is shown by transmission electron microscopy. The alumina grains are columnar with grain widths increasing from 22±7 to 41±9 nm, as the temperature increases from 280 to 560 °C. This is consistent with a surface diffusion dominated growth mode and suggests that -alumina deposition at low temperatures is possible once initial grain nucleation has occurred. Results are also presented demonstrating chromia/-alumina growth on a technological substrate (Haynes230 Ni-based super alloy, Haynes International, Inc.).

The effects of substitutional additives on the properties and phase stability of - and -alumina (Al₂O₃), are investigated by density functional theory total energy calculations. The dopants explored are 5 at. % of Cr, Mo, Co, and As substituting for Al, respectively, N and S substituting for O, in the and lattices. Overall, the results show that it is possible to shift, and even reverse, the relative stability between - and -alumina by substitutional additives. The alumina bulk moduli are, in general, only slightly affected by the dopants but density of states profiles reveal additional peaks in the alumina band gaps. We also show that phase separations into pure oxides are energetically favored over doped alumina formation, and we present results on a number of previously unstudied binary oxides.

The deposition flux obtained during reactive radio frequency magnetron sputtering of an Al target in Ar/O₂ gas mixtures was studied by mass spectrometry. The results show significant amounts of molecular AlO⁺ (up to 10% of the Al⁺ flux) in the ionic flux incident onto the substrate. In the presence of ~10–4 Pa H₂O additional OH⁺ and AlOH⁺ were detected, amounting to up to about 100% and 30% of the Al⁺ flux, respectively. Since the ions represent a small fraction of the total deposition flux, an estimation of the neutral content was also made. These calculations show that, due to the higher ionization probability of Al, the amount of neutral AlO in the deposition flux is of the order of, or even higher than, the amount of Al. These findings might be of great aid when explaining the alumina thin film growth process.

The ion flux obtained during reactive magnetron sputtering of an Al target in Ar/O₂ gas mixtures was studied by energy-resolved mass spectrometry, as a function of the total and O₂ partial pressures. The positive ions of film-forming species exhibited bimodal energy distributions, both for direct current and radio frequency discharges, with the higher energy ions most likely originating from sputtered neutrals. For the negative oxygen ions a high-energy peak was observed, corresponding to ions formed at the target surface and accelerated towards the substrate over the sheath potential. As the total pressure was increased the high-energy peaks diminished due to gas-phase scattering. Based on these results, the role of energetic bombardment for the phase constituent of alumina thin films are discussed.

In this work, physical phenomena related to the growth and phase formation of alumina, Al₂O₃, are investigated by experiments and computer calculations. Alumina finds applications in a wide variety of areas, due to many beneficial properties and several existing crystalline phases. For example, the α and κ phases are widely used as wear-resistant coatings due to their hardness and thermal stability, while, e.g., the metastable γ and θ phases find applications as catalysts or catalyst supports, since their surface energies are low and, hence, they have large surface areas available for catalytic reactions.

The metastable phases are involved in transition sequences, which all irreversibly end in the transformation to the stable α phase at about 1050 °C. As a consequence, the metastable aluminas, which can be grown at low temperatures, cannot be used in high temperature applications, since they are destroyed by the transformation into α. In contrast, α-alumina, which is the only thermodynamically stable phase, typically require high growth temperatures (~1000 °C), prohibiting the use of temperature sensitive substrates. Thus, there is a need for increasing the thermal stability of metastable alumina and decreasing the growth temperature of the α phase.

In the experimental part of this work, hard and single-phased α-alumina thin films were grown by magnetron sputtering at temperatures down to 280 °C. This dramaticdecrease in growth temperature was achieved by two main factors. Firstly, the nucleation stage of growth was controlled by pre-depositing a chromia “template” layer, which is demonstrated to promote nucleation of α-alumina. Secondly, it is shown that energetic bombardment was needed to sustain growth of the α phase. Energy-resolved mass spectrometry measurements demonstrate that the likely source of energetic bombardment, in the present case, was oxygen ions/atoms originating from the target surface. Overall, these results demonstrate that low-temperature α-alumina growth is possible by controlling both the nucleation step of growth as well as the energetic bombardment of the growing film. In addition, the mass spectrometry studies showed that a large fraction of the deposition flux consisted of AlO molecules, which were sputtered from the target. Since the film is formed by chemical bonding between the depositing species, this observation is important for the fundamental understanding of alumina thin film growth.

In the computational part of the work, the effect of additives on the phase stability of α- and θ-alumina was investigated by density functional theory calculations. A systematic study was performed of a large number of substitutional dopants in the alumina lattices. Most tested dopants tended to reverse the stability between α- and θ-alumina; so that, e.g., Modoping made the θ phase energetically favored. Thus, it is possible to stabilize the metastable phases by additives. An important reason for this is the physical size of the dopant ions with respect to the space available within the alumina lattices. For example, large ions induced θ stabilization, while ions only slightly larger than Al, e.g., Co and Cu, gave a slight increase in the relative stability of the α phase. We also studied the stability of some of these compounds with respect to pure alumina and other phases, containing the dopants, with the result that phase separations are energetically favored and will most likely occur at elevated temperatures.

Low-temperature growth (500 °C) of α-Al₂O₃ thin films by reactive magnetron sputtering was achieved for the first time. The films were grown onto Cr₂O₃ nucleation layers and the effects of the total and O₂ partial pressures were investigated. At 0.33 Pa total pressure and ≥ 16 mPa O₂ partial pressure α-Al₂O₃ films formed, while at lower O₂ pressure or higher total pressure (0.67 Pa), only γ phase was detected in the films (which were all stoichiometric). Based on these results we suggest that α phase formation was promoted by a high energetic bombardment of the growth surface. This implies that the phase content of Al₂O₃ films can be controlled by controlling the energy of the depositing species. The effect of residual H₂O (10^− 4 Pa) on the films was also studied, showing no change in phase content and no incorporated H (< 0.1%). Overall, these results are of fundamental importance in the further development of low-temperature Al₂O₃ growth processes.

Optical modeling of one folded tandem solar cell and four types of stacked tandem solar cells has been performed using the finite element method and the transfer matrix method for the folded cell and the stacked cells, respectively. The results are analyzed by comparing upper limits for short circuit currents and power conversion efficiencies. In the case of serial connected tandems all of the five cell types may be compared, and we find that the folded cells are comparable to stacked tandem cells in terms of currents and power conversion efficiencies.

The high power impulse magnetron sputtering (HiPIMS) discharge brings about increased ionization of the sputtered atoms due to an increased electron density and efficient electron energization during the active period of the pulse. The ionization is effective mainly within the electron trapping zone, an ionization region (IR), defined by the magnet configuration. Here, the average extension and the volume of the IR are determined based on measuring the optical emission from an excited level of the argon working gas atoms. For particular HiPIMS conditions, argon species ionization and excitation processes are assumed to be proportional. Hence, the light emission from certain excited atoms is assumed to reflect the IR extension. The light emission was recorded above a 100 mm diameter titanium target through a 763 nm bandpass filter using a gated camera. The recorded images directly indicate the effect of the magnet configuration on the average IR size. It is observed that the shape of the IR matches the shape of the magnetic field lines rather well. The IR is found to expand from 10 and 17 mm from the target surface when the parallel magnetic field strength 11 mm above the racetrack is lowered from 24 to 12 mT at a constant peak discharge current.

This report describes the successful application of a combinatorial chemistry approach to the evaluation of the amorphous transparent oxide semiconductor Al-In-Zn-O, a-AIZO, for use as channel layers in thin film transistors, TFTs. Many technologies, such as computing and electronic displays, rely on the use of the transistor. In particular, for flat panel displays, the development of new TFTs for the control electronics are necessary for thinner displays with better resolution. In addition, transparent materials deposited at low temperatures would enable a new range of applications. To accomplish this, new materials for the TFT channel layer are needed.

Transparent oxide semiconductors (TOS) are one alternative the silicon based materials currently in use and the first TOS, amorphous In-Ga-Zn-O, has just gone into production. However, despite its good properties, it suffers from the disadvantage of containing the scarce and expensive metals In and Ga. Several attempts have been made to replace Ga with Al but no systematic study of a-AIZO has been reported. This report describes such a study, using a method known as combinatorial chemistry.

Initially, a-AIZO thin films with composition gradients were deposited by DC/RF magnetron sputtering and, following characterization, TFTs with a variety of a-AIZO channel layer composition were manufactured and investigated. Two different compositional areas were found to yield TFTs with good characteristics.

Highly size-controllable synthesis of free-standing perfectly crystalline silicon carbide nanocrystals has been achieved for the first time through a plasma-based bottom-up process. This low-cost, scalable, ligand-free atmospheric pressure technique allows fabrication of ultra-small (down to 1.5 nm) nanocrystals with very low level of surface contamination, leading to fundamental insights into optical properties of the nanocrystals. This is also confirmed by their exceptional photoluminescence emission yield enhanced by more than 5 times by reducing the nanocrystals sizes in the range of 1-5 nm, which is attributed to quantum confinement in ultra-small nanocrystals. This method is potentially scalable and readily extendable to a wide range of other classes of materials. Moreover, this ligand-free process can produce colloidal nanocrystals by direct deposition into liquid, onto biological materials or onto the substrate of choice to form nanocrystal films. Our simple but efficient approach based on non-equilibrium plasma environment is a response to the need of most efficient bottom-up processes in nanosynthesis and nanotechnology.