Full Paper

Time-Resolved Ionisation Studies of the

High Power Impulse Magnetron Discharge
in Mixed Argon and Nitrogen Atmosphere
Arutiun P. Ehiasarian,* Yolanda Aranda Gonzalvo, Terry D. Whitmore
Magnetron sputtering technology is widely used to grow thin films on a range of substrate
materials. High power impulse magnetron sputtering (HIPIMS) technology differentiates itself
from other types of magnetron sputtering by the high degree of ionisation of the sputtered
material achieved by applying high peak powers of 3 kW
cm2 (4 A
cm2) at duty cycles of
<1%. The current paper discusses HIPIMS of Ti in mixed argon and nitrogen atmosphere,
commonly used for hard coatings deposition. Estimation of the composition of the ion
deposition flux arriving at the substrate position is extracted from energy-resolved mass
spectrometry data. The measured time-resolved ion mass and ion energy distribution functions were compared for the HIPIMS discharge and industry-standard direct current (DC) and
medium frequency pulsed DC magnetron discharges operated at the same average power of
2 W
cm2. In inert Ar atmosphere, HIPIMS produced a metal-dominated ion flux with Ti1
concentration of 46%, compared to 10% in DC operation. In reactive atmosphere of Ar and
10% N2 the HIPIMS discharge produced an ion flux with significantly increased content of
ionised film-forming species such as Ti1, Ti2 and N1. The atomic ion N1 was the most
abundant species representing 40% of the total flux with Ti1 19% and Ar1 19%. In contrast,
the ion flux in DC and pulsed DC discharges was dominated by Ar1 and molecular ion N1
2 .
Introduction
High power impulse magnetron sputtering (HIPIMS) is a
new method for physical vapour deposition (PVD) based
on magnetron sputtering.[1,2] It utilises transient impulse
(short pulse) glow discharges with very high power and
current density (up to 3 kW
cm2 and 4 A
cm2,
respectively, at a duty cycle of <5%). Under these conditions the plasma density near the target increases sufficiently to ionise a significant proportion of the sputtered
metal ions[2,3] thus creating a high-efficiency metal ion

A. P. Ehiasarian
Nanotechnology Centre for PVD Research, Materials and Engineering Research Institute, Sheffield Hallam University, Howard
St., Sheffield S1 1WB, UK
Fax: (44) 114 225 3646
E-mail: A. Ehiasarian@shu.ac.uk
Y. A. Gonzalvo, T. D. Whitmore
Plasma & Surface Analysis Division, Hiden Analytical Ltd., 420
Europa Boulevard, Warrington WA5 7UN, UK
Plasma Process. Polym. 2007, 4, S309S313
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

source. The discharge has been up scaled successfully[4]

and has found a number of applications. One example is
substrate pretreatment under HIPIMS which benefits from
droplet-free metal ion bombardment that provides a
highly clean coatingsubstrate interface where local epitaxial growth is maintained.[5] This in turn enhances the
coating adhesion. Other example are CrN films grown by
HIPIMS with a high density of the microstructure that
demonstrated superior performance in corrosion and wear
environments.[6,7]
The HIPIMS discharge is known to develop in two phases
within each power pulse. Fast time-resolved optical
emission spectroscopy (OES) studies have demonstrated
a transition from gas phase to metal phase.[2,8] OES has also
shown the existence of high proportions of ions and the
presence of doubly charged species.[2] Mass-spectroscopy
results in inert gas atmosphere have indicated high metal
ion content and high ion energy.[3]
Although nitride films grown by HIPIMS in reactive
atmosphere have demonstrated a superior performance
which has been linked to the high content of N1
2 observed

DOI: 10.1002/ppap.200730806

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A. P. Ehiasarian, Y. A. Gonzalvo, T. D. Whitmore

in OES studies,[6] quantitative characterisation of the discharge in reactive conditions has not been published to
date.
The current paper utilises an energy-resolved mass spectrometer to characterise quantitatively the composition,
energy and time evolution of the ions in the HIPIMS
plasma in reactive atmosphere. The results are discussed in
relation with conventional direct current (DC) and midfrequency (MF) pulsed DC sputtering at the same average
power and composition of the atmosphere.

performed at an average power of 200 W and pulse frequency of

20 kHz.
The measurements in inert gas atmosphere were done at an Ar
pressure of 2.5  103 mbar. The reactive sputtering was done
at partial pressures of Ar PAr 2.5  103 mbar and N2PN2 2 
104 mbar.

Results
The time-averaged ion energy distribution function (IEDF)
for the HIPIMS, DC and pulsed DC discharges was
measured.

Experimental Part
HIPIMS in Inert and Reactive Atmosphere
The experiments were performed in an ultra high vacuum (UHV)
chamber with a base pressure of <109 mbar. One magnetron
(TorusTM, Kurt J. Lesker) with a diameter of 75 mm was furnished
with a Ti target and operated in HIPIMS, DC and MF pulsed DC
(pulsed DC for short) mode. Figure 1 is a schematic cross-section of
the set-up. The energy-resolved mass spectrometer (PSM003,
Hiden Analytical Ltd.) was situated at the substrate positionat a
distance of 120 mm from the target and angled at 588 with respect
to the target normal. The plasma was sampled through a 200 mm
grounded orifice. The acceptance angle of 58 did not allow a line of
sight to the surface of the target. The collection was gated with a
TTL output from the power supply and was adjusted to measure
for a 70 ms window centred at the peak of the 150 ms pulse.
Time-resolved measurements were collected at 70 ms intervals by
shifting the measurement window in time. The delay in detection
due to flight time through the spectrometer was considered
according to the mass charge ratio of each species. The differences
in flight times between species were smaller than the time step
used. This allowed a quantification of the ion flux composition by
normalising the count rates for each ion to the sum of all ions for
each time step.
The HIPIMS discharge was operated at a peak power of 20 kW,
average power of 200 W and frequency of 100 Hz. The current
pulse duration was 150 ms, the peak current was 50 A and the
discharge voltage was 550 V for inert gas atmosphere and 480 V
for reactive gas mixture. DC and MF pulsed DC sputtering were

Figure 1. Schematic cross-section of the UHV system indicating

the positions of the cathode and plasma sampling mass spectrometer.

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2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 2(a) shows IEDFs of species measured for HIPIMS of Ti

in Ar atmosphere. Singly ionised Ti1 was the strongest
signal with a relative content of 46%. Together with Ti2,
metal ions comprise 60% of the total ion flux. The maximum
energy measured for Ti1 was 45 eV for 99.9% of ions. Gas
ions had significantly lower energies with maximum of 10
and 40 eV for Ar1 and Ar2, respectively. These energies are
lower than reported previously[3] for ions travelling parallel
to the target. The discrepancies could be attributed to the
different geometry of measurements.

Figure 2. IEDFs of ions generated in HIPIMS of Ti discharges in

(a) inert Ar and (b) reactive Ar/N2 atmosphere.

DOI: 10.1002/ppap.200730806

Time-Resolved Ionisation Studies of the High Power Impulse Magnetron Discharge . . .

In reactive atmosphere, the dominating species

were N1 single atom species comprising 40% of the total
ion flux. Some 30% can be attributed to Ti1 and Ti2. The
IEDFs for all the ions were shifted to higher energy as
shown in Figure 2(b). The dominant ions N1 have a
maximum energy of 40 eV for 99.9% of particles. Ti1
and Ti2 reach maximum energies of 35 and 50 eV,
respectively, and Ar ions reach 20 eV. It is interesting to
note that the plasma potential, as derived from the maximum in the IEDFs, remains low at approximately 5 V.

DC and Pulsed DC Sputtering

IEDFs for DC and pulsed DC sputtering in the same Ar N2
mixture are shown in Figure 3(a) and 3(b). The ion count
rate and respectively, the ionisation in pulsed DC is higher
than for DC. However, both the ion chemistry and the
IEDFs are quite similar. Here the maximum energies for
99.9% of the ions are less than 10 eV and correspond well
with a Maxwellian distribution. In contrast to the HIPIMS
case, the content of Ti1 is 3% and Ti2 is negligible. The
content of N1 is also strongly reduced, indicating a significantly lower degree of activation of both the pulsed DC
and DC plasmas.
Table 1 shows a comparison of average plasma composition for HIPIMS, pulsed DC and DC sputtering. It can be
seen that the nitrogen atomic ion and metallic ions have a
significantly higher contribution in HIPIMS than DC and
pulsed DC.
The general trend is that the ion flux in HIPIMS contains
factor of 5 more Ti1 and Ti2 metal ions than pulse DC or DC
technologies. The ratio holds for both inert and reactive gas
atmospheres. The activation of the reactive gas is significant
with HIPIMS generating factor of four times more N1
dissociated ions than DC and DC technologies.
Figure 2(b) and Table 1 show that the ion flux in HIPIMS
comprises mainly N1 and Ti1. These ions represent
film-forming species and as such determine directly the
growth conditions with their energy. In contrast, in DC
sputtering, the majority of ions are Ar1 who only contributes
part of their energy indirectly via bombardment collisions

with the Ti and N atoms that have already nucleated at the

surface or are in the process of surface diffusion.
Figure 4(a) shows IEDF for Ti1 measured in inert
atmosphere for HIPIMS, pulsed DC and DC. It is immediately obvious that the count rate is two orders of
magnitude higher for HIPIMS indicating a higher ion flux
during the pulse. The average energy is a factor of 2 greater
for HIPIMS. A similar trend is observed for the N1 ions as
shown in Figure 4(b).
Both the average and maximum energies of ions in
HIPIMS are a factor of 3 higher in comparison to conventional DC and pulsed DC sputtering. Since these energies
are significantly higher than what is expected from
sputtering of solid targets at the impingement energies
discussed, alternative mechanisms should be considered. A
certain increase in energy can be expected due to the
increase in sputter voltage from 300 to 500 V, however this
alone cannot account for the three-fold increase observed.
The time-averaged measurements were performed for the
duration of the HIPIMS power pulse only, i.e. excluding
the times of switching on and off of the voltage. During
these periods, abrupt changes in the sheath may cause
surges in plasma potential and the generation of high
energy ions as has been measured for pulsed DC discharges.[9] Since the high energy metal ions are generated
during the pulse, this mechanism is excluded as the
plasma is close to equilibrium and the sheaths change
relatively slowly.
A possible explanation can be sought in the transport of
metal ions. As metal ions are created in the dense plasma
region near the cathode, they may be accelerated back to
the target to take part in a self-sputtering process. A
fraction of these metal ions may be reflected from the
surface with a high energy thus creating fast neutrals. A
similar process is known to occur in conventional
sputtering where approximately 20% of Ar ions can be
reflected as fast neutrals with energy of the order of up to
200 eV.[10] The fast Ti neutrals however have to traverse
through the HIPIMS plasma again where the density is so
high[2] that they may be ionised a second time by electron
collisions. This ionisation path will not change the energy
of the ion and as a result the process will generate high

Table 1. Ion content in per cent of the total ion flux.

Gas composition

Ar1R

Ar2R

HIPIMS

Ar

34

46

15

Pulse DC

Ar

78

13

0.2

Technology

DC

Ti1R

Ti2R

N1R
2

N1R

Ar

82

11

0.2

HIPIMS

Ar R N2

19

19

10

40

Pulse DC

Ar R N2

52

0.07

31

DC

Ar R N2

65

0.03

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2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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A. P. Ehiasarian, Y. A. Gonzalvo, T. D. Whitmore

Figure 3. IEDFs of ions generated in (a) DC and (b) MF pulsed DC

sputtering of Ti discharges in reactive Ar/N2 atmosphere.

energy ions as observed in the Ti1 IEDF. A similar

mechanism may be responsible for the high energy of N1
and Ar2 species.
Time Evolution During the Pulse
The time evolution of the HIPIMS plasma was measured
for inert and reactive gas atmospheres.
Inert Gas Atmosphere
The time evolution in inert gas atmosphere is given in
Figure 5(a). The data are normalised to 1. The evolution can
be separated into two parts. Initially the discharge consists
of singly and doubly ionised Ar. After 70 ms, the Ti1
and Ti2 ions comprise the majority of ion fluxsome 70%
of the total. This phase coincides with the peak in
discharge current and extends over 100 ms. At this time
the Ar1 and Ar2 content diminish quickly due to the
intense production of metal ions and the rarefaction of the
gas by the high power dissipated in the pulse. At the end of
the pulse at 150 ms the power is switched off and the metal
signal decays as the voltage is insufficient to sustain the

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2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Figure 4. IEDFs of the film-forming species: (a) Ti1 and (b) N1 for
HIPIMS (triangles), MF pulsed DC (squares) and conventional DC
sputtering (circles) for Ti.

sputtering process. The plasma comprises mainly Ar ions

generated by remnant electrons that ionise the gas present
in the chamber and electron waves generated during the
power pulse and reflected by the chamber walls.[11] These
observations fit well with published OES results measured
for Cr, showing the transition from a gas discharge to a
metal discharge phase.[2] However, the present results
illustrate the point in a quantitative manner and
demonstrate the relatively high content of metal ions
generated by HIPIMS.
Reactive Gas Atmosphere
The time evolution in reactive gas atmosphere is presented
in Figure 5(b). Here again the discharge is initiated as a gas
plasma containing mainly N1 ions (55%) but also N1
2
and Ar1 ions comprising 10% each. The N1 signals are
observed to drop and at the same time the Ti1 and Ti2
metal ion count rate is observed to peak together with the
power pulse. This indicates the transition from a gas
plasma to a metal plasma thus diminishing the relative
amount of gas ions at the moment of maximum metal ion
content. Once power is switched off at the end of pulse, Ti

DOI: 10.1002/ppap.200730806

Time-Resolved Ionisation Studies of the High Power Impulse Magnetron Discharge . . .

high powers dissipated heat up the working gas thus

causing it to expand resulting in depletion of the local
source of gas ions. In this way it is not surprising that at the
peak of metal creation (highest plasma density), the gas
ion signal is depleted. As illustrated in Figure 4(a) and 4(b)
the mechanism operates identically in both inert and
reactive atmospheres.

Conclusion

Figure 5. Mass-spectroscopic data on time evolution of an HIPIMS

of Ti discharge in inert (a) and reactive (b) gas atmospheres.

ions diminish quickly while N2 and Ar ions remain due to

electrons existing in the decaying plasma.
In summary, the initial gas plasma phase is generated
by a short electron wave of duration of <5 ms travelling
from the target through the chamber.[11] These electrons
are probably free electrons that are outside the electromagnetic field trap at the target surface and who are
affected by the high voltage applied to the cathode due to
absence of a sheath are at the beginning of the pulse. Once
electrons start to ionise the working gas, plasma is formed
and a sheath is established near the cathode. The subsequent
ionisation occurs near the target due to the strong confinement. The density of N1
is negligible as compared
2
to N1 density indicating that electron impact dissociation
controls the nitrogen dissociation for low pressures. The
dissociation of N2 by electron impact is the major source of
atomic nitrogen for the HIPIMS plasma in comparison with
the DC and DC pulsed cases in reactive gas atmosphere.
As sufficient gas ions are created, they bombard the
target and sputter away metal atoms. By this time the
plasma density is quite high, with the target current exceeding 1 A
cm2 and the metal atoms are ionised with a
high probability as they traverse this high-density plasma.
The process of metal ionisation is so efficient that doubly
charged metal ions were detected with high signal intensity even at the substrate position. In the mean time, the
Plasma Process. Polym. 2007, 4, S309S313
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The composition and energy of the ion flux in HIPIMS,

pulsed DC and DC discharges were investigated quantitatively in inert (Ar) and reactive gas (Ar N2) atmospheres.
The ion flux in HIPIMS was found to contain factor of 5
more metal ions and factor of 4 more reactive nitrogen ions
compared to conventional sputtering techniques. The
film-forming species of Ti and N were present in ionised
form in HIPIMS thus allowing high control over the
deposition conditions. IEDFs revealed factor of 3 higher
average energies for the HIPIMS case due to the ionisation
of reflected fast neutrals of both gas and metal.
The time evolution of an HIPIMS pulse in reactive gas
atmosphere was similar to inert gas atmosphere. Distinct
stages of gas-dominated and metal-dominated plasma
were detected. The peak metal ion content was 60% for the
inert gas case and 30% for the reactive gas case.
Acknowledgements: The authors gratefully acknowledge the
financial support of the EU project INNOVATIAL and EPSRC grant
EP/D049202/1.
Received: September 12, 2006; Revised: December 15, 2006;
Accepted: December 20, 2006; DOI: 10.1002/ppap.200730806
Keywords: high density plasma; ion-assisted deposition; ionenergy distribution function (IEDF); magnetron
[1] V. Kouznetsov, K. Macak, J. M. Schneider, U. Helmersson,
I. Petrov, Surf. Coat. Technol. 1999, 122(23), 290.
[2] A. P. Ehiasarian, R. New, W.-D. Munz, L. Hultman,
U. Helmersson, V. Kouznetsov, Vacuum 2002, 65(2), 147.
[3] J. Bohlmark, J. Alami, C. Christou, A. P. Ehiasarian,
U. Helmersson, J. Vac. Sci. Technol. A 2005, A23(1), 18.
[4] A. P. Ehiasarian, R. Bugyi, Proc. 47th Annual Technical Conference of the Society of Vacuum Coaters, San Francisco, April
2004, 437.
[5] W.-D. Munz, A. P. Ehiasarian, P. E. Hovsepian, EP 02 011 204.1,
2001.
[6] A. P. Ehiasarian, W.-D. Munz, L. Hultman, U. Helmersson,
I. Petrov, Surf. Coat. Technol. 2003, 163164, 267.
[7] A. P. Ehiasarian, P. E. Hovsepian, L. Hultman, U. Helmersson,
Thin Solid Films 2004, 457(2), 270.
[8] K. Macak, V. Kouznetsov, J. Schneider, U. Helmersson,
I. Petrov, J. Vac. Sci. Technol. A 2000, A18(4), 1.
[9] A. Vetushka, S. K. Karkari, J. W. Bradley, J. Vac. Sci. Technol.
2004, A22(6), 2459.
[10] W. D. Westwood, Sputter Deposition, AVS, New York 2003.
[11] J. Bohlmark, J. T. Gudmundsson, J. Alami, M. Latteman,
U. Helmersson, IEEE Trans. Plasma Sci. 2005, 33(2 I), 346.

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