| 1. |
- Aijaz, Asim, 1980-
(författare)
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Synthesis of Carbon-based and Metal-Oxide Thin Films using High Power Impulse Magnetron Sputtering
- 2014
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 2. |
- Ekeroth, Sebastian, 1988-
(författare)
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Plasma Synthesis and Self-Assembly of Magnetic Nanoparticles
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Nanomaterials are important tools for enabling technological progress as they can provide dramatically different properties as compared to the bulk counterparts. The field of nanoparticles is one of the most investigated within nanomaterials, thanks to the existing, relatively simple, means of manufacturing. In this thesis, high-power pulsed hollow cathode sputtering is used to nucleate and grow magnetic nanoparticles in a plasma. This sputtering technique provides a high degree of ionization of the sputtered material, which has previously been shown to aid in the growth of the nanoparticles. The magnetic properties of the particles are utilized and makes it possible for the grown particles to act as building blocks for self-assembly into more sophisticated nano structures, particularly when an external magnetic field is applied. These structures created are termed “nanowires” or “nanotrusses”, depending on the level of branching and inter-linking that occurs.Several different elements have been investigated in this thesis. In a novel approach, it is shown how nanoparticles with more advanced structures, and containing material from two hollow cathodes, can be fabricated using high-power pulses. The dual-element particles are achieved by using two distinct and individual elemental cathodes, and a pulse process that allows tuning of individual pulses separately to them. Nanoparticles grown and investigated are Fe, Ni, Pt, Fe-Ni and Ni-Pt. Alternatively, the addition of oxygen to the process allows the formation of oxide or hybrid metal oxide – metal particles. For all nanoparticles containing several elements, it is demonstrated that the stoichiometry can be easily varied, either by the amount of reactive gas let into the process or by tuning the amount of sputtered material through adjusting the electric power supplied to the different cathodes.One aim of the presented work is to find a suitable material for the use as a catalyst in the production of H2 gas through the process of water splitting. H2 is a good candidate to replace fossil fuels as an energy carrier. However, rare elements (such as Ir or Pt) needs to be used as the catalyst, otherwise a high overpotential is required for the splitting to occur, leading to a low efficiency. This work demonstrates a possible route to avoid this, by using nanomaterials to increase the surface-to-volume ratio, as well as optimizing the elemental ratio between different materials to lower the amount of noble elements required.
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| 3. |
- Lansåker, Pia, 1968-
(författare)
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Gold-Based Nanoparticles and Thin Films : Applications to Green Nanotechnology
- 2012
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The use of gold-based nanoparticles and thin films is very promising when it comes to improving several green nanotechnologies. Therefore, in order to further their use in applications such as electrochromic devices, photovoltaics, light-emitting diodes and photocatalysis, the aim of this work was to study the growth of gold-based nanoparticles and thin films.All depositions were made using DC magnetron sputtering, and optical, structural, electrochemical, electrical and photocatalytic studies of the films and particles were performed.The various applications yield a variety of substrate properties, and how these substrate properties affect gold coalescence was studied by depositing gold on glass slides and on SnO2:In, ITO and TiO2 base layers.Temperature also affects the gold coalescence. Therefore, gold was deposited on heated and non-heated substrates, where the latter were also post-heated, with a temperature range between 25ºC and 140ºC in both cases. Various temperatures were also used for manufacturing gold nanoparticles, and their effect as photocatalytic improvers was tested on WO3 films.The optical properties of Au films on glass were determined by ellipsometry in the 0.25 – 2 µm range, and then a spectral density analysis was performed of the effective dielectric permittivity.This work showed that thin gold films are excellent replacements for oxide-based transparent conductors in electrochromic devices. It was also shown that thin homogeneous gold films were better conductors when they were deposited on glass, compared to when they were deposited on oxide base layers, regardless of the optical, electrical and structural properties, or the doping concentration of the base layers.The results also showed that thin gold films were durable at 76ºC, and hence hold for a typical window temperature of ~70ºC. For higher temperatures, gold deposition on heated and non-heated substrates resulted in a distinct difference in growth, and there was also a distinct difference between post-heated gold films produced at 25ºC, compared to when the films were deposited on heated substrates. In the latter case, an island structure was obtained at 140ºC.Spectral density analysis gave spectral densities of similar shape for nanoparticles and continuous gold films, which is useful information for further investigations.
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| 4. |
- Lundin, Daniel
(författare)
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The HiPIMS Process
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The work presented in this thesis involves experimental and theoretical studies related to a thin film deposition technique called high power impulse magnetron sputtering (HiPIMS), and more specifically the plasma properties and how they influence the coating. HiPIMS is an ionized physical vapor deposition technique based on conventional direct current magnetron sputtering (DCMS). The major difference between the two methods is that HiPIMS has the added advantage of providing substantial ionization of the sputtered material, and thus presents many new opportunities for the coating industry. Understanding the dynamics of the charged species and their effect on thin film growth in the HiPIMS process is therefore essential for producing high-quality coatings.In the first part of the thesis a new type of anomalous electron transport was found. Investigations of the transport resulted in the discovery that this phenomenon could quantitatively be described as being related and mediated by highly nonlinear waves, likely due to the modified two-stream instability, resulting in electric field oscillations in the MHz-range (the lower hybrid frequency). Measurements in the plasma confirmed these oscillations as well as trends predicted by the theory of these types of waves. Using electric probes, the degree of anomalous transport in the plasma could also be determined by measuring the current density ratio between the azimuthal current density (of which the Hall current density is one contribution) and the discharge current density, Jϕ / JD. The results were verified in another series of measurements using Rogowski probes to directly gain insight into the internal currents in the HiPIMS discharge. The results provided important insights into understanding the mechanism behind the anomalous transport.It was furthermore demonstrated that the current ratio Jϕ / JD is inversely proportional to the transverse resistivity, η⊥ , which governs how well momentum in the direction of the current is transferred from the electrons to the ions in the plasma. By looking at the forces involved in the charged particle transport it was expected that the azimuthally rotating electrons would exert a volume force on the ions tangentially outwards from the circular race track region. The effect of having an anomalous transport would therefore be that the ions were transported across the magnetic field lines and to a larger extent deflected sideways, instead of solely moving from the target region towards a substrate placed in front of the target some distance away. From the experiments it was confirmed that a substantial fraction of sputtered material is transported radially away from the cathode and lost to the walls in HiPIMS as well as in DCMS, but more so for HiPIMS giving one possible explanation to why the deposition rate is lower for HiPIMS compared to DCMS. Moreover, in a separate investigation on the energy flux it could be determined that the heating due to radial energy flux reached as much as 60 % of the axial energy flux, which is likely a result of the anomalous transport of charged species present in the HiPIMS discharge. Also, the recorded ion energy flux confirmed theoretical estimations on this type of transport regarding energy and direction.In order to gain a better understanding of the complete discharge regime, as well as providing a link between the HiPIMS and DCMS processes, the current and voltage characteristics were investigated for discharge pulses longer than 100 μs. The current behavior was found to be strongly correlated with the chamber gas pressure. Based on these experiments it was suggested that high-current transients commonly seen in the HiPIMS process cause a depletion of the working gas in the area in front of the target, and thereby a transition to a DCMS-like high voltage, lower current regime, which alters the deposition conditions.In the second part of the thesis, using the results and ideas from the fundamental plasma investigations, it was possible to successfully implement different coating improvements. First, the concept of sideways deposition of thin films was examined in a dual-magnetron system providing a solution for coating complex shaped surfaces. Here, the two magnetrons were facing each other having opposing magnetic fields forcing electrons, and thereby also ionized material to be transported radially towards the substrate. In this way deposition inside tubular substrates can be made in a beneficial way.Last, the densification process of thin films using HiPIMS was investigated for eight different materials (Al, Ti, Cr, Cu, Zr, Ag, Ta, and Pt). Through careful characterization of the thin film properties it was determined that the HiPIMS coatings were approximately 5-15 % denser compared to the DCMS coatings. This could be attributed to the increased ion bombardment seen in the HiPIMS process, where the momentum transfer between the growing film and the incoming ions is very efficient due to the equal mass of the atoms constituting the film and the bombarding species, leading to a less pronounced columnar microstructure. The deposition conditions were also examined using a global plasma model, which was in good agreement with the experimental results.
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| 5. |
- Viloan, Rommel Paulo B., 1988-
(författare)
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Engineered ion-bombardment as a tool in thin film deposition
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Energetic-ion bombardment has become an attractive route to modify the crystal growth and deposit high quality thin films. In high-power impulse magnetron sputtering (HiPIMS) where the discharge is characterized by a significant amount of ions of the sputter-ejected atoms, energetic-ion bombardment effects could not be underestimated. This is due to a combination of ions with better mass match to the growing film and reduced incorporation of the working gas. The ions of the sputtered species in HiPIMS also exhibit a broad ion energy distribution function (IEDF), which increases the average energy of the ion flux. However, the IEDF of a HiPIMS discharge is still dominated by ions with energies corresponding to thermalized species. While it is common to use a substrate bias to increase the energy of the incoming ion flux, some deposition set-up make it challenging or even impossible to apply a substrate bias. Hence, it is important to come up with techniques to address such problem. In this thesis, strategies to increase the energy of the ions in a HiPIMS discharge without any substrate bias were investigated and thin films were deposited to evaluate the effects on the crystal growth and film properties.By varying the power per pulse (Ppulse) in a HiPIMS discharge for the deposition of TiN, it was found that the amount of Ti2+ ions could be effectively tuned. The increase in the amount of Ti2+ correlated well with an increase in the film compressive stress, though an optimum Ppulse could be identified in which the stress is relatively low and hardness is high. The results also indicate a broad IEDF for ions of the sputtered species (Ti+, Ti2+, N+) and narrow IEDF for ions of the working gas (Ar+, Ar2+, N2+). However, using such strategy results to an increase in the average ion energy only within the range of <25 eV.Operating a HiPIMS discharge in bipolar mode, where a positive pulse voltage (Urev) is immediately applied after the main HiPIMS pulse, results to ion acceleration due to an increase in the plasma potential to values close to Urev. A simple model is proposed indicating that ion acceleration occurs at a region in between the target and the grounded substrate. Further IEDF measurements with bipolar HiPIMS with varying length of the main HiPIMS pulse (τneg) and length of the positive pulse (τpos) indicate that most of the acceleration happens at the sheath in front of a grounded substrate. By varying τneg and τpos, it was shown that the fraction of accelerated ions can be optimized such that almost all ions are accelerated when τneg is relatively short and τpos is sufficiently long. The growth of TiN films indicate an increase in the compressive stress, hardness and density with an increase in Urev, typical for films deposited using energetic-ion bombardment. Finally, Cu depositions indicate that, due to the pulsed nature of Urev and since most of the ion acceleration happens at the substrate sheath, bipolar HiPIMS process can be compared to a conventional HiPIMS pulse with a synchronized pulsed bias, which has the same timing as the applied positive pulse.
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| 6. |
- Gunnarsson, Rickard
(författare)
-
Controlling the growth of nanoparticles produced in a high power pulsed plasma
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Nanotechnology can profoundly benefit our health, environment and everyday life. In order to make this a reality, both technological and theoretical advancements of the nanomaterial synthesis methods are needed. A nanoparticle is one of the fundamental building blocks in nanotechnology and this thesis describes the control of the nucleation, growth and oxidation of titanium particles produced in a pulsed plasma. It will be shown that by controlling the process conditions both the composition (oxidationstate) and size of the particles can be varied. The experimental results are supported by theoretical modeling.If processing conditions are chosen which give a high temperature in the nanoparticle growth environment, oxygen was found to be necessary in order to nucleate the nanoparticles. The two reasons for this are 1: the lower vapor pressure of a titanium oxide cluster compared to a titanium cluster, meaning a lower probability of evaporation, and 2: the ability of a cluster to cool down by ejecting an oxygen atom when an oxygen molecule condenses on its surface. When the oxygen gas flow was slightly increased, the nanoparticle yield and oxidation state increased. A further increase caused a decrease in particle yield which is attributed to a slight oxidation ofthe cathode. By varying the oxygen flow, it was possible to control the oxidation state of the nanoparticles without fully oxidizing the cathode. Pure titanium nanoparticles could not be produced in a high vacuum system because oxygen containing gases such as residual water vapour have a profound influence on nanoparticle yield and composition. In an ultrahigh vacuum system titanium nanoparticles without significantoxygen contamination were produced by reducing the temperature of the growth environment and increasing the pressure of an argon-helium gas mixture within whichthe nanoparticles grew. The dimer formation rate necessary for this is only achievable at higher pressures. After a dimer has formed, it needs to grow by colliding with a titanium atom followed by cooling by collisions with multiple buffer gas atoms. The condensation event heats up the cluster to a temperature much higher than the gas temperature, where it is during a short time susceptible to evaporation. When the clusters’ internal energy has decreased by collisions with the gas to less than the energy required to evaporate a titanium atom, it is temporarily stable until the next condensation event occurs. The temperature difference by which the cluster has to cool down before it is temporarily stable is exactly as many kelvins as the gas temperature.The addition of helium was found to decrease the temperature of the gas, making it possible for nanoparticles of pure titanium to grow. The process window where this is possible was determined and the results presented opens up new possibilities to synthesize particles with a controlled contamination level and deposition rate.The size of the nanoparticles has been controlled by three means. The first is to change the electrical potential around the growth zone, which allows for size (diameter) control in the order of 25 to 75 nm without influencing the oxygen content of the particles. The second means is by increasing the pressure which decreases the ambipolar diffusion rate of the ions resulting in a higher growth material density. By doing this, the particle size can be increased from 50 to 250 nm, however the oxygen content also increases with increasing pressure when this is done in a high vacuum system. The last means of size control was by adding a helium flow to the process where higher flows resulted in smaller nanoparticle sizes.When changing the pressure in high vacuum, the morphology of the nanoparticles could be controlled. At low pressures, highly faceted near spherical particles were produced. Increasing the pressure caused the formation of cubic particles which appear to ‘fracture’ at higher pressures. At the highest pressure investigated, the particles became poly-crystalline with a cauliflower shape and this morphology was attributed to a lowad atom mobility.The ability to control the size, morphology and composition of the nanoparticles determines the success of applying the process to manufacture devices. In related work presented in this thesis it is shown that 150-200 nm molybdenum particles with cauliflower morphology were found to scatter light in which made them useful in photovoltaic applications, and the size of titanium dioxide nanoparticles were found to influence the selectivity of graphene based gas sensors.
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| 7. |
- Mickan, Martin, 1989-
(författare)
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Deposition of Al-doped ZnO films by high power impulse magnetron sputtering
- 2017
-
Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Transparent conducting oxides (TCOs) are an important class of materials with many applications such as low emissivity coatings, or transparent electrodes for photovoltaics and flat panel displays. Among the possible TCO materials, Al-doped ZnO (AZO) is studied due to its relatively low cost and abundance of the raw materials. Thin films of AZO are commonly produced using physical vapour deposition techniques such as magnetron sputtering. However, there is a problem with the homogeneity of the films using reactive direct current magnetron sputtering (DCMS). This homogeneity problem can be related to the bombardment of the growing film with negative oxygen ions, that can cause additional acceptor defects and the formation of insulating secondary phases. In this work AZO films are deposited by high power impulse magnetron sputtering (HiPIMS), a technique in which high instantaneous current densities are achieved by short pulses of low duty cycle.In the first part of this thesis, the possibility to improve the homogeneity of the deposited AZO films by using HiPIMS is demonstrated. This improvement can be related to the high instantaneous sputtering rate during the HiPIMS pulses, so the process can take place in the metal mode. This allows for a lower oxygen ion bombardment of the growing film, which can help to avoid the formation of secondary phases. Another problem of AZO is the stability of the properties in humid environments. To assess this problem, the degradation of the electrical properties after an aging procedure was investigated for films deposited by both DCMS and by HiPIMS. A method was proposed, to restore the properties of the films, using a low temperature annealing under N2 atmosphere. The improvement of the electrical properties of the films could be related to a diffusion process, where water is diffusing out of the films. Then, the influence of the substrate temperature on the properties of AZO films deposited by HiPIMS was studied. The electrical, optical and structural properties were found to improve with increasing substrate temperature up to 600 ◦C. This improvement can be mostly explained by the increase in crystalline quality and the annealing of defects. Finally, the deposition of AZO films on flexible PET substrates was investigated. The films are growing as a thick porous layer of preferentially c-axis oriented columns on top of a thin dense seed layer. The evolution of the sheet resistance of the films after bending the films with different radii was studied. There is an increase in the sheet resistance of the films with decreasing bending radius, that is less pronounced for thicker films.
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| 8. |
- Wallin, Erik, 1979-
(författare)
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Alumina Thin Films : From Computer Calculations to Cutting Tools
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The work presented in this thesis deals with experimental and theoretical studies related to alumina thin films. Alumina, Al2O3, is a polymorphic material utilized in a variety of applications, e.g., in the form of thin films. However, controlling thin film growth of this material, in particular at low substrate temperatures, is not straightforward. The aim of this work is to increase the understanding of the basic mechanisms governing alumina growth and to investigate novel ways of synthesizing alumina coatings. The thesis can be divided into two main parts, where the first part deals with fundamental studies of mechanisms affecting alumina growth and the second part with more application-oriented studies of high power impulse magnetron sputter (HiPIMS) deposition of the material.In the first part, it was shown that the thermodynamically stable α phase, which normally is synthesized at substrate temperatures of around 1000 °C, can be grown using reactive sputtering at a substrate temperature of merely 500 °C by controlling the nucleation surface. This was done by predepositing a Cr2O3 nucleation layer. Moreover, it was found that an additional requirement for the formation of the α phase is that the depositions are carried out at low enough total pressure and high enough oxygen partial pressure. Based on these observations, it was concluded that energetic bombardment, plausibly originating from energetic oxygen, is necessary for the formation of α-alumina (in addition to the effect of the chromia nucleation layer). Moreover, the effects of residual water on the growth of crystalline films were investigated by varying the partial pressure of water in the ultra high vacuum (UHV) chamber. Films deposited onto chromia nucleation layers exhibited a columnar structure and consisted of crystalline α-alumina if deposited under UHV conditions. However, as water to a partial pressure of 1*10-5 Torr was introduced, the columnar α-alumina growth was disrupted. Instead, a microstructure consisting of small, equiaxed grains was formed, and the γ-alumina content was found to increase with increasing film thickness.To gain a better understanding of the atomistic processes occurring on the surface, density functional theory based computational studies of adsorption and diffusion of Al, O, AlO, and O2 on different α-alumina (0001) surfaces were also performed. The results give possible reasons for the difficulties in growing the α phase at low temperatures through the identification of several metastable adsorption sites and also show how adsorbed hydrogen might inhibit further growth of α-alumina crystallites. In addition, it was shown that the Al surface diffusion activation energies are unexpectedly low, suggesting that limited surface diffusivity is not the main obstacle for low-temperature α-alumina growth. Instead, it is suggested to be more important to find ways of reducing the amount of impurities, especially hydrogen, in the process and to facilitate α-alumina nucleation when designing new processes for low-temperature deposition of α-alumina.In the second part of the thesis, reactive HiPIMS deposition of alumina was studied. In HiPIMS, a high-density plasma is created by applying very high power to the sputtering magnetron at a low duty cycle. It was found, both from experiments and modeling, that the use of HiPIMS drastically influences the characteristics of the reactive sputtering process, causing reduced target poisoning and thereby reduced or eliminated hysteresis effects and relatively high deposition rates of stoichiometric alumina films. This is not only of importance for alumina growth, but for reactive sputter deposition in general, where hysteresis effects and loss of deposition rate pose a substantial problem. Moreover, it was found that the energetic and ionized deposition flux in the HiPIMS discharge can be used to lower the deposition temperature of α-alumina. Coatings predominantly consisting of the α phase were grown at temperatures as low as 650 °C directly onto cemented carbide substrates without the use of nucleation layers. Such coatings were also deposited onto cutting inserts and were tested in a steel turning application. The coatings were found to increase the crater wear resistance compared to a benchmark TiAlN coating, and the process consequently shows great potential for further development towards industrial applications.
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| 9. |
- Aiempanakit, Montri, 1977-
(författare)
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Reactive High Power Impulse Magnetron Sputtering of Metal Oxides
- 2013
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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| 10. |
- Aijaz, Asim
(författare)
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HiPIMS-based Novel Deposition Processes for Thin Films
- 2012
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- 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.
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