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Using an energy-resolved mass spectrometer and a time-resolved Langmuir probe, the distribution of bombarding ion energies, their fluxes and energy fluxes at a substrate in an asymmetric bi-polar pulsed DC magnetron have been determined. The discharge was operated in Ar at a pressure of 0.53 Pa with a Ti target and pulsed DC frequencies of 100 and 350 kHz with a range of duty cycles (from 50 to 96%). At 100 kHz, the Ar + and Ti + time-averaged ion energy distribution functions (IEDFs) reveal three peaks, which are at low energy (<10 eV), in a mid-range (20-50 eV) and at high energy (60-100 eV). We correlate these peaks with distinct phases of the discharge voltage. At 350 kHz the IEDFs show four peaks reflecting a more complex voltage waveform. The low-energy ions are generated in the 'on' phase when the plasma potential is typically a few volts above ground. The Ti + energy spectra show a remnant of the original sputter-neutral energy distribution function. The mid-range ions are produced in the quiescent region of the voltage reverse phase, when the plasma potential is raised globally a few volts above the cathode potential, typically 10-30 V. The high-energy ions are generated in a period of ∼0.3 µs, during the discharge voltage overshoot, when the target potential rises to typically over +140 V. However, given the time resolution of the Langmuir probe (0.5 µs), it is not possible to determine if plasma potential is lifted globally to this high potential or only close to the cathode. At 350 kHz, these 'fast' ions make up to about a quarter of the total ion flux at the substrate and an upper bound transient power flux of about 2.5 times the maximum delivered in the 'on' phase. The total power flux to a substrate in the sustained phase of the discharge is found to increase with frequency and reverse time.

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The application of mid-frequency (100–350 kHz) pulsed dc power at the substrate is a recent development in the magnetron sputtering field. It has been found that, unlike the dc case, if the bias is pulsed in this range, the current drawn at the substrate does not saturate, but continues to increase with increasing bias voltage. In addition, this effect becomes more marked as the pulse frequency is increased. For example, under a particular set of operating conditions, a threefold increase in ion current was observed at a bias voltage of −300 V when the bias was pulsed at 350 kHz, compared to the dc case. This phenomenon is believed to be due to the initiation of a second discharge at the substrate. Pulsing the substrate bias voltage, therefore, offers a novel means of controlling the ion current drawn at the substrate. Clearly, this has significant implications in relation to film growth, sputter cleaning, and substrate preheating processes. Consequently, the variation in ion current with pulse frequency and bias voltage has been studied for an unbalanced magnetron sputtering system. In addition, substrate heating rates, current–voltage wave forms and plasma characteristics have also been investigated. A series of TiO2 and TiN films were then grown under different bias conditions. Analysis of these films showed that the application of pulsed dc power at the substrate can significantly influence film structure and properties. In particular, shifts in crystalline structure and texture were observed.