The effect on the energy distributions of metal and gas ions in a bipolar high-power impulse magnetron sputtering (HiPIMS) discharge as the negative and positive pulse lengths are altered are reported. The results presented demonstrate that the selection of the pulse lengths in a HiPIMS discharge is important in optimizing the amount of accelerated ions. A short enough negative pulse is needed so that ions do not escape to the substrate before being accelerated by the positive pulse that follows the main negative HiPIMS pulse. The length of the positive pulse should also be long enough to accelerate the majority of the ions, but a too long positive pulse depletes the process chamber of electrons so much that it makes it difficult to initiate the next HiPIMS pulse. When pulse lengths of negative and positive pulses are properly selected, the fraction of ions, both metal and gas, accelerated by the positive pulse voltage is close to 100 %.
High power impulse magnetron sputtering (HiPIMS) is an ionized physical vapor deposition technique, providing a high flux of metal ions to the substrate. However, one of the disadvantages for industrial use of this technique is a reduced deposition rate compared to direct current magnetron sputtering (dcMS) at equal average power. This is mainly due to a high target back-attraction probability of the metal ions with typical values in the range 70%–90% during the pulse. In order to reduce this effect, we focused on the contribution of ion fluxes available immediately after each HiPIMS pulse; a time also known as afterglow. Without a negative potential on the target at this stage of the HiPIMS process, the back-attracting electric field disappears allowing remaining ions to escape the magnetic trap and travel toward the substrate. To quantify the proposed mechanism, we studied the effect of HiPIMS pulse duration on the outward flux of film-forming species in titanium discharges, which are known to exhibit more than 50% reduction in deposition rate compared to dcMS. By shortening the HiPIMS pulse length, it was found that the contribution to the outward flux of film-forming species from the afterglow increases significantly. For example, HiPIMS discharges at a constant peak current density of about 1.10 A cm−2 showed a 45% increase of the deposition rate, by shortening the pulse duration from 200 to 50 μs. Ionized flux fraction measurements, using a gridless quartz crystal micro-balance-based ion meter, showed that this increase of the deposition rate could be achieved without compromising the ionized flux fraction, which remained approximately constant. The key to the achieved optimization of HiPIMS discharges lies in maintaining a high peak discharge current also for short pulse lengths to ensure sufficient ionization of the sputtered species.
The plasma potential at a typical substrate position is studied during the positive pulse of a bipolar high-power impulse magnetron sputtering (bipolar HiPIMS) discharge with a Cu target. The goal of the study is to identify suitable conditions for achieving ion acceleration independent on substrate grounding. We find that the time-evolution of the plasma potential during the positive pulse can be separated into several distinct phases, which are highly dependent on the discharge conditions. This includes exploring the influence of the working gas pressure (0.3 – 2 Pa), HiPIMS peak current (10 – 70 A corresponding to 0.5 – 3.5 A/cm2), HiPIMS pulse length (5 – 60 μs) and the amplitude of the positive voltage U+ applied during the positive pulse (0 – 150 V). At low enough pressure, high enough HiPIMS peak current and long enough HiPIMS pulse length, the plasma potential at a typical substrate position is seen to be close to 0 V for a certain time interval (denoted phase B) during the positive pulse. At the same time, spatial mapping of the plasma potential inside the magnetic trap region revealed an elevated value of the plasma potential during phase B. These two plasma potential characteristics are identified as suitable for achieving ion acceleration in the target region. Moreover, by investigating the target current and ion saturation current at the chamber walls, we describe a simple theory linking the value of the plasma potential profile to the ratio of the available target electron current and ion saturation current at the wall.
In this paper, the prospects of iron oxide films and their sulfidation for dye-sensitized solar cells (DSSC) are reviewed. Iron oxide thin films were prepared by hollow cathode plasma jet (HCPJ) sputtering, with an admixture of oxygen in the argon working gas and with an iron nozzle as the sputtering target. The discharge was powered by a constant current source in continuous mode and by a constant voltage source in pulsed mode. Plasma composition was measured by an energy-resolved mass spectrometer. Moreover, secondary electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), absorption and Raman spectra of the films are presented. Strong correlation between the color of the iron oxide film and its phase composition was revealed. Iron oxide films were sulfided at 350 °C. A relatively clean pyrite phase was obtained from the magnetite, while the marcasite with admixture of the pyrite phase was obtained from the hematite. Low influence of sulfidation on the films’ microstructure was demonstrated.
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