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Ground state atomic oxygen in high-power impulse magnetron sputtering: a quantitative study

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2017 J. Phys. D: Appl. Phys. 50 075204

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 Journal of Physics D: Applied Physics

J. Phys. D: Appl. Phys. 50 (2017) 075204 (13pp) doi:10.1088/1361-6463/aa560c

Ground state atomic oxygen in high-

power impulse magnetron sputtering:
a quantitative study
NikolayBritun1, AlexandrBelosludtsev2, TiagoSilva3 and RonySnyders1,4
1
Chimie des Interactions Plasma-Surface (ChIPS), CIRMAP, Universit de Mons, 23 Place du Parc,
B-7000 Mons, Belgium
2
Department of Physics and NTIS, University of West Bohemia, Univerzitn 8, 306 14 Plze, Czechia
3
Instituto de Plasmas e Fusao Nuclear, Instituto Superior Tecnico, Universidade de Lisboa, 1049-001
Lisboa, Portugal
4
Materia Nova Research Center, Parc Initialis, B-7000 Mons, Belgium

E-mail: nikolay.britun@umons.ac.be

Received 29 October 2016, revised 8 December 2016

Accepted for publication 29 December 2016
Published 25 January 2017

Abstract
The ground state density of oxygen atoms in reactive high-power impulse magnetron
sputtering discharges has been studied quantitatively. Both time-resolved and space-resolved
measurements were conducted. The measurements were performed using two-photon
absorption laser-induced fluorescence (TALIF), and calibrated by optical emission actinometry
with multiple Ar emission lines. The results clarify the dynamics of the O ground state atoms
in the discharge afterglow significantly, including their propagation and fast decay after the
plasma pulse, as well as the influence of gas pressure, O2 admixture, etc.

Keywords: HiPIMS, reactive sputtering, atomic oxygen, number density, density calibration,
TALIF, optical emission spectroscopy

(Some figuresmay appear in colour only in the online journal)

1.Introduction
As a result of the evolution of sputtering discharges, magne
tron sputtering (MS) brought essential advantages to thin film
science and technology during the 1960s [1, 2]. In MS dis
charges, sputtering from a solid cathode is greatly enhanced
(compared to cathode sputtering) by placing constant magnets
under the cathode, which allows electrons to be trapped, thus
improving the sputtering rate significantly. Reactive magne
tron sputtering (RMS) represents a further step in the evo
lution of magnetron discharges. It involves sputtering with a
reactive gas (such as O2, N2, etc) as an admixture to the main
working gas (typically Ar), and thus covers a wide number of
applications related to composite thin films [3, 4].
The numerous benefits of pulsed magnetron sputtering
(often referred to as pulsed direct current magnetron sput
tering, or pulsed DCMS) [5] led to the appearance of
so-called high-power impulse magnetron sputtering (HiPIMS)
discharges in the early 1990s [6, 7]. These belong to the so-
called ionized physical vapor deposition (IEPVD) discharges
[8, 9] and represent a further step [6] of DCMS evolution as
a result of the time redistribution of the applied power by
squeezing the plasma pulse and significantly elevating the
pulse power while maintaining the time-averaged applied
power at a level that is comparable to that in the DCMS case
[7]. The pulse repetition frequency in HiPIMS ranges roughly
from 0.05 to several kHz, whereas the pulse duration stays
within the few s to few hundred s range. At the same time,
the duty ratio does not exceed a few per cent. As a result, the
ionization degree in HiPIMS is significantly elevated during
the plasma on-time, compared to DCMS [9]. The HiPIMS pro
cess is now widely recognized for industrial applications due
to the unique coating properties that can be obtained, such as
high film density, controllable phase constitution, etc [10, 11].
Reactive HiPIMS (R-HiPIMS) discharges, like reactive DCMS
ones, use O2, N2, etc admixtures to the working gas for the

1361-6463/17/075204+13$33.00 1 2017 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 50 (2017) 075204
Figure 1. Top (a) and side (b) views of the HiPIMS reactor with the optical diagnostic alignment used in this work.
synthesis of oxide, nitride, etc coatings, which are currently
being investigated intensively [10, 1214].
The problem of quantification of the atomic density of
reactive gas, as well as its flux, in sputtering plasmas is
important. Knowing the number density of the O, N, etc
atoms produced in the plasma bulk and trapped by a growing
film surface would clarify our understanding of the film
structure significantly, in respect of its surface chemistry,
surface morphology and other properties [11]. It might also
be helpful for modeling plasma and film growth. Detailed
knowledge of the flux of O (N, etc) atoms to the surface
would also be extremely useful for controlling film stoi
chiometry, since the methods for determining the particle
velocity in magnetron discharges are rather well-developed
in both the DCMS [15, 16] and HiPIMS [17] cases. In addi
tion, providing the fluxes of the reactive atomic species to
the film surface are known, the mentioned atomic reac
tive species can be delivered artificially to the film surface,
with them being produced in a separate plasma source [18].
This type of atom delivery should enhance film stoichiom
etry control significantly, while at the same time potentially
decreasing target poisoning.
To date, apart from experimental and modeling studies on
the O metastable atoms in R-HiPIMS [19], there has been a
significant lack of experimental data for the ground state O
density. The main reason for this is the difficulty of meas
uring the O ground state density directly by optical absorption
spectroscopy, which is a straightforward non-intrusive tech
nique used for this purpose [20]. In the case of ground state O,
this technique requires a deep ultraviolet (UV) region, which
involves expensive vacuum UV (VUV) spectrometers [21].
The calibration of the O density using Xe gas in combination
with the two-photon absorption laser-induced fluorescence
(TALIF) technique [22] represents another expensive alterna
tive, with its own disadvantages related to the gas rarefaction
in HiPIMS discharges [9, 17, 23]. Indeed, using Xe gas alone
(i.e. without plasma), the local character of the calibration will
be lost due to the gas rarefication in the presence of HiPIMS
discharges, which should be taken into account separately in
this case.
2
N Britun etal
Thus, an easy-to-implement calibration method would be
beneficial for reactive gas atom number density determina
tion in magnetron discharges. Regarding this, the aim of this
work was to quantify the density of the ground state O in the
HiPIMS case in both time and space using the methods of
visible-infrared spectroscopy. In order to keep the discharge
unperturbed, non-intrusive spectral diagnostic techniques,
combining laser-based spectroscopy and optical emission
spectroscopy, were chosen. This paper is organized as fol
lows. After a short description of the experimental setup, the
theoretical background of the proposed calibration methods is
given, followed by the results obtained under various HiPIMS
discharge conditions. Finally, brief conclusions summarize
the work.
2. Experimental part
2.1. The HiPIMS reactor
The measurement and calibration of the O atom density in
HiPIMS plasma were both performed in a stainless steel
vacuum chamber with a magnetron source with a circular
planar cathode (target), 10cm in diameter and 5mm thick,
as described elsewhere [17]. The HiPIMS discharge operated
in an ArO2 gas mixture in a pressure range of 320 mTorr
at a total gas flow ranging between 10 and 80 (typically 44)
standard cubic centimeters per minute (sccm) with a repeti
tion frequency of 100 Hz and a pulse duration of 50 s. Side
and top views of the described vacuum reactor with the pur
pose of O atom detection and calibration are given in figure1.
The relevant discharge parameters are summarized in table1.
The typical current (I) and voltage (V) waveforms for metallic
and poisoned discharge modes for the studied metallic targets
(Ti, W, Cu, Ag) are given in figure2. The observed differences
in the current and voltage waveforms are the result of changes
related to metal ion (in the metallic mode) versus Ar ion (in
the poisoned mode) dominated sputtering, as well as changes
in the ion-induced secondary electron emission (ISEE) coef
ficients in these modes, as analyzed in [24]. The discharge
pulse energy EP (defined as EP = V (t )I (t )dt, where V (t )
0
J. Phys. D: Appl. Phys. 50 (2017) 075204 N Britun etal

Table 1. Main parameters for the HiPIMS discharge used in this

work.
Parameter Value
HiPIMS pulse repetition rate 100 Hz
HiPIMS pulse duration 50 s
Working pressure 320 mTorr
O2 flow fraction range 540%
HiPIMS pulse energy (EP) 0.5 J (typically)
Distance to target (OES) 5cm (typically)
OES measurement time delay 50 s

and I (t ) are the voltage and current profiles respectively, is

the pulse duration, and t is time) was real-time monitored by
a Tektronics DPO3054 digital oscilloscope and ranged from
0.2 to 1.2 J per pulse. The typically used value of EP=0.5
J corresponds to a pulse-averaged power of10 kW and a
pulse-averaged current density of0.25 A cm2.

2.2. The O atom detection

The detection of O(3P2) ground state atoms during the

HiPIMS afterglow (plasma-off time) was organized using
the TALIF technique, in accordance with the standard exci
tation scheme with the laser radiation at about 225.6nm and
the fluorescence at 844.6nm. The detailed parameters for
this technique can be found in table2, or elsewhere [22, 25].
The measurements were performed using a pulsed Sirah
dye laser with a pulse duration of5 ns and a repetition
frequency of 10 Hz at the second harmonics (attained with
Coumarin 450 dye solution). The fundamental harmonic of
the dye laser was real-time monitored and locked using a
Figure 2. The HiPIMS currentvoltage waveforms acquired by a
HighFinesse WS6-200 wavemeter that produced a relative digital oscilloscope in metallic and poisoned HiPIMS modes using
wavelength drift of about 4 107 during the measurements various sputtering targets at 20 mTorr of Ar pressure and EP=0.5 J.
(see table2).
The measurement and calibration points were located Table 2. Parameters for the TALIF experimental setup used for
O atom detection.
~5cm above the target surface, as shown in figure1(b). An
Andor iStar DH740-18F intensified charge coupled device TALIF parameter Value
(ICCD) camera in the image accumulation mode was used
Excitation wavelength (theory) 225.58 nm
as a detector for both the OES and TALIF cases. About 300 Measured wavelength (first harmonic) 441.1815nm160 fm
laser pulses were averaged for each TALIF data point. A Laser pulse energy inside reactor 0.10.3 mJ
Nikkor 50mm f/1.4 D lens with an optical bandpass filter Laser beam waist section 0.4mm0.4 mm
(840nm central wavelength and 10nm bandwidth) repre Volume of measurements 0.1cm3
sented the imaging lens. In order to acquire the O TALIF Averaged laser photon density (waist) 3 1015 cm3
signal, the imaging data were averaged in the region of TALIF measurement delay time 509000 s
interest (ROI), followed by background fitting and subtrac Distance to target (z) range 2565 mm
tion, as shown schematically in figure 3. The laser beam
was focalized above the target by an f/50mm fused silica
lens in order to increase the photon density in the ROI. The to an Andor SR750 spectrometer with the above-mentioned
laser pulse energy inside the vacuum chamber varied from ICCD and were averaged along the line-of-sight about 5cm
0.2 to 0.5 mJ, corresponding to the average photon density above the target (see figure1). The line-of-sight in this case
in the beam waist of ~3 1015 cm3. The variations of the was represented by a slowly divergent cone with a diameter
laser energy during the measurements were compensated of ~1.5cm above the target. A corresponding spectral cor
using the real-time monitored laser energy data, similarly rection that took the spectral response of the fiber+mono
to [17]. chromator+ICCD system into account was applied to all the
The optical emission spectroscopy (OES) measurements OES measurements. The spectral resolution used was about
were performed at the end of the plasma pulse (i.e. at 50 s 0.02nm in the case of the electron temperature measurements
of time delay) using a visible-infrared optical fiber connected and about 0.05nm otherwise.

3
J. Phys. D: Appl. Phys. 50 (2017) 075204
Figure 3. (a) The appearance of the O TALIF signal on the ICCD
sensor, along with the dedicated ROI. (b) The background fitting
and subtraction procedure used in this work.
3. O density calibration methods
In this work two spectroscopic techniques, one based on
optical emission and one based on optical absorption spectr
oscopy, are proposed for quantification of the O atom density
in HiPIMS discharges. Both of them are based on the optical
actinometry principle.
3.1. Optical emission actinometry
Optical actinometry is a well-known non-intrusive technique
that allows us to determine the absolute density of species by
the ratio of spectral emission lines [26]. In this case, a certain
amount of a foreign gas (called the actinometer) with a known
concentration is added to the gas mixture. This technique
has numerous applications, e.g. determining the CO density
in microwave plasma [27], etc. Its principle is based on the
fact that the emission intensity Iij corresponding to a particular
spectral transition between the upper (i) and lower (j) atomic
or molecular states is proportional to the population of the
upper state (see e.g. [28, 29]). Assuming that electron impact
is the dominant excitation mechanism, for the transition light
intensity we can write:
Iij = ChijAij ni = ChijAij
(1) nk n ekki /
Aik + Qi,
k<i k<i
4
N Britun etal
where C is a constant related to the detection system, hij is the
quantum of light corresponding to the ij radiative transition,
Aij is the coefficient of spontaneous emission, k < i nk n ekki
describes the electron excitation of the level i coming from
all the lower levels with densities nk, n e is the electron den
sity, kki is the electron impact excitation coefficient for k-i
excitation, k < i Aik represents the radiative losses from the
upper level i, and Qi is the collisional quenching of the level i,
defined as Qi = j nijkQji (the summation goes over all the rel
evant quenchers of the level i with densities n jand quenching
rates kQji). The electron impact excitation coefficient can be
expressed in the form [29]:
kki =
(2) f () ()d, 0
where f () is the electron energy distribution function
(EEDF), () is the electron impact excitation cross-section
and 0 is the electron excitation threshold for this transition.
In low-pressure discharges (mTorr range) for radiative trans
itions the collisional quenching can be neglected compared to
the radiative de-excitation. In addition, the first sum in expres
sion (1) is normally reduced to the n 0 n e k 0i term representing
the electron excitation from the ground state level (the so-
called corona approximation). While this approximation works
in most low-pressure discharge cases [27], in some cases the
contribution of the intermediate metastable levels should also
be taken into account. In particular, in the case of Ar-containing
discharges, which are relevant to this work, the contribution
of the Ar 4s 1sx (x=5,4,3,2) states can be essential, starting
from several mTorr, as studied by Boffard etal [30]. Taking into
account these considerations, the expression (1) yields:
Iij = ChijAij n 0n ek 0i(1 + met )/
(3) Aik ,
where n 0 denotes the ground state density and
met (k nk kki )/(n 0 k 0i ) is the relative contribution of the
metastable states to the population of the i excited state. In
this case the summation covers the relevant metastable levels
k<i.
Based on equation (3), the expression giving the ground
state number density of the species of interest (n0x) through
the ground state number density of the actinometer (nact 0 ) can
be obtained by making a ratio of the corresponding emission
lines:
n0x
(4) =
I ijx ijx Aijact k act act
0i (1 + met )
Aikx.
I ijact ijact Aijx k 0xi (1 + met
x
nact
0 ) act
Aik
Since in our case n0x = [O] and nact
0 = [Ar], neglecting the
x
contribution of O metastables (met = 0), for the ground state
O atom density we obtain:
[O] = [Ar] Ract (1 + Ar
(5) met ) ij ,
where some terms are redefined as Ract I ijx /I ijact (i.e. the emis
sion peaks ratio), and
J. Phys. D: Appl. Phys. 50 (2017) 075204 N Britun etal

Table 3. Spectral transitions used for calibration of the O ground

state density by emission actinometry.
Ar upper Wavelength
state (nm) ij (at Te=2eV) Ar a
met (from [30] )

2p1 750.39 0.42 0.06

2p2 826.45 0.05 0.21
727.29 0.007
696.54 0.02
2p3 840.82 0.1 0.23
738.40 0.04
706.72 0.02
2p5 751.47 0.11 0.13
a
The estimations are performed at 15 mTorr, taking into account both Ar
metastable and resonant states and assuming that the Ar 1s5 density is equal
to 5 1010 cm3 (top estimation).

ijx Aijact k act

ij act x 0xi
(6)
Aikx
.
ij Aij k 0i act
Aik
Following the work of Boffard etal [30], where the rela
tive contributions from the Ar 4s group to the Ar excited states
are analyzed, only the Ar spectral transitions with a minimal
contribution from Ar metastables were chosen for this study,
as summarized in table3. The top estimated values of the Ar
(at 15 mTorr) are also shown in table3. The typical density of
the Ar metastables for this estimation was determined based
on separate measurements.
We have to note that the accuracy of optical actinometry
depends strongly on the electron temperature Te. This is
related to the fact that the electron impact excitation coeffi
cient k 0i is sensitive to this parameter when Te<3eV, which
falls in the typical Te range for magnetron plasmas. This effect
is illustrated in figure 4(a), where the ratios of the electron
excitation coefficients k 0Ari /k O0i for several Ar excited states are
presented. The electron cross-section data in this case are
taken from [31, 32]. In our case, Te was determined exper
imentally using the Ar spectral peak ratio method proposed
by Silva etal [33]. In our case, the calculations of the electron
impact excitation coefficients were performed at Te=2eV
(see section 4.1) assuming a Maxwellian EEDF, which is a
good approximation for HiPIMS plasmas [9, 34]. Indeed, the
non-thermal (hot) electrons that may be present in the HiPIMS
plasma pulse likely play a minor role in our case, since our
measurement point is chosen at the end of the plasma pulse,
whereas the hot electrons mainly exist at the beginning of the
pulse. The EEDF changes to a single-slope Maxwellian dis
tribution at the end of the HiPIMS pulse, where Te is typically
about 2eV, as studied by Poolcharuansin etal [35]. The quick
disappearance of the hot electrons during the HiPIMS pulse is
also confirmed by our recent LIF observations [17].
In addition to the electron temperature, the gas temper
ature is also important, as estimates of the Ar ground state
density are involved in the described calibration procedure.
This temperature was taken to be equal to 550K at the end
of the plasma pulse, based on [36]. The Ar, etc ground state
densities were estimated using the ideal gas laws assuming
uniform pressure in the discharge volume.
met
Figure 4. (a) The ratio of the electron excitation coefficients for
O(3p 3PJ) and Ar(4p 2px) excited states as a function of electron
temperature, calculated using the available cross-section data [31].
(b) The electron impact excitation cross-sections for the Ar (1s5)
[31] and O (3s 5 S20) [54] metastable states, along with a Maxwellian
EEDF (at Te=2eV). The ratio of Ar and O excitation coefficients
(shown by dashed areas, representing the corresponding integrals)
in this case is equal to 0.93.
3.2. Optical absorption actinometry
During the discharge afterglow the actinometry principle
can still be applied to the non-radiative (metastable) upper
states. Since in pulsed magnetron discharges the population
of metastable states can be significant for both O [19] and Ar
[17, 37] atoms, the principles of emission actinometry can be
transferred to the metastable levels. Since the number den
sities of the corresponding metastable states are normally
determined by atomic absorption spectroscopy [37, 38], the
proposed method can be called absorption actinometry. This
method is supposed to be particularly useful in the HiPIMS
afterglow, when plasma emission is vanishingly small, the
electron excitation is negligible and the metastable state popu
lations can be reliably determined by absorption techniques in
the UVinfrared spectral range [19, 3740].
Let us consider two metastable states of the atom of interest
and the actinometer (O and Ar in our case). During the plasma
pulse they are both populated by electron excitation and, by
the definition of metastable states, they are only depopu
lated by collisional quenching (in the first approximation).
Assuming there are no intermediate metastable levels between
the ground state level and the considered metastable levels,
the ratio of their populations during the plasma on-time can
be written as:

5
J. Phys. D: Appl. Phys. 50 (2017) 075204 N Britun etal

Table 4. Comparison of the O atom ground state density

determined by the optical absorption actinometry and emission
actinometry methods, as proposed in this work (in the ArTi
40%O2 HiPIMS discharge working at 1kHz, 20 mTorr, EP=0.3 J
and pulse duration=20 s).
Time [O]emiss.
delay [O met ] / [Ar met] [O2] [O]abs.actinom. actinom.
a

50 s 0.1 3 1014 cm3 2.4 1013 cm3 1.4

1013 cm3
100 s 0.2 3 1014 cm3 1.7 1013 cm3 1.4
1013 cm3
0
Figure 5. The evolution of the Ar (1s5) and O (3s 5 S2) metastable 200 s 0.8 3 10 cm
14 3
9 10 cm
12 3
1 1013
state densities measured in the ArTi40% O2 HiPIMS discharge cm3
by optical absorption spectroscopy. Repetition frequency=1kHz,
pulse duration=20 s, gas pressure=20 mTorr and EP=0.3 J. a
The emission actinometry is applied at the end of a 20 s plasma pulse (in
The density fits in the afterglow are shown by the dashed lines. The the 1kHz, 20 mTorr and EP=0.3 J ArTi HiPIMS discharge). Afterwards
vertical dashed line corresponds to the end of the plasma pulse. the results are extrapolated to the afterglow using the O density trends
Adapted from [55]. shown in figure15.

The O density estimates through absorption actinometry

nO0met [O] k Oex.met Qmet
Ar
(7) = , are made based on the number densities of Ar (3p5 4s1 1s5
Ar
n0met [Ar] k ex.met
Ar
QOmet referred to as the Ar 1s5 state below) and O (3s 5 S22) metastable
where nO0met and n0met
Ar
are the populations of the corresponding states measured by absorption spectroscopy in an R-HiPIMS
metastable states at the end of the plasma pulse or right at the discharge operating at 1kHz at 20 mTorr in a TiAr40% O2
beginning of the afterglow, k O,Ar gas mixture at EP=0.3 J. The obtained density evolutions for
ex.met are their electron excitation
coefficients and QO,Ar are the quenching coefficients of these these conditions are given in figure5. The results for O density
met
estimation using the absorption actinometry method at different
states.
time delays in the 1kHz discharge are given in table4, where
The electrons cool down rather quickly in the HiPIMS
they are compared (approximately) to the emission actinom
afterglow and electron excitation can normally be neglected
etry results obtained for the same discharge conditions. The
about a hundred s after the plasma pulse [41]. Due to this
obtained discrepancies between the two methods are within
fact, the metastable states should be depopulated exponen
a factor of two, which may be due to (i) the low stability of
tially at a rate mainly defined by their quenching coefficients:
the absorption measurements applied for O and Ar metastable
n met (t ) = n 0met Exp(t Qmet ),
(8) state density determination, (ii) the strong role of the electron
where t is the time from the beginning of the afterglow. excitation at short time delays after the plasma pulse, (iii) the
influence of the Ar 1s5 state on the population of O metastable
Combining (7) and (8) and redefining nOmet(t ) = [O met ] and
states during the afterglow (Ar met+ O Ar +O met) and (iv)
nAr
met (t ) = [Ar
met
], for the O ground state density we obtain:
the uncertainties of the emission actinometry method. In our
Ar
[O met ] k ex.met QOmet Ar
opinion, more careful absorption measurements of the Ar and
[(9)
O] =[Ar] Exp(t (Qmet QOmet)). O metastable state density performed during the afterglow
[Ar met] k Oex.met QAr met
time could increase the precision of the absorption actinometry
It can be shown that for the two considered Ar and O meta technique, making it comparable to that of TALIF. This might
Ar virtually eliminate the necessity of having a bulky laser setup
stable states, k ex.met /k Oex.met1 at Te 2 eV, as illustrated in
for the determination of O ground state density.
figure4(b). Taking into account the fact that molecular oxygen
can be considered as the main quencher at high O2 admix
tures, whereas quenching by Ar can be neglected [42, 43], 4. Results and discussion
we can write QO,Ar O,Ar O
met = [O2] k q.met (wherek q.met=1.4 10
10
Ar
cm3 s1 [44] and k q.met =2.1 1010 cm3 s1 [45] are the 4.1. Electron temperature
quenching rates of the considered O and Ar states by O2, and The electron temperature in this work is determined at the end
[O2] is the O2 ground state density). In this case, the final of the HiPIMS pulse using the following expression (see [33]):
expression for the O atom ground state density through the
population of the metastable states in the afterglow can be Te = (7.04 N (1s5)0.10 )
written in the form:  0.19
Log 1/(6.03 17.86 N (1s5)0.17),
R
(11)
O
[O met ] k q.met Ar where R is the intensity ratio of the Ar 425.9nm and
Ar Exp(t [O2] (k q.met
[O] = [Ar] k Oq.met)).
[Ar met] k q.met 750.4nm emission lines (corresponding to the Ar 3p11s2
(10) and 2p11s3 transitions, respectively) and N(1s5) is the

6
J. Phys. D: Appl. Phys. 50 (2017) 075204
Figure 6. The appearance of the Ar 425.94nm emission peak
acquired for the case of (a) Ag, (b) Ti, (c) Cu and (d) W targets with
a spectral resolution of about 0.02nm showing the peak distortion
by the surrounding spectral lines [46].
population of the Ar 1s5 state normalized to the Ar ground
state density. The relative error of Te calculated by expression
(11) is supposed to be about 10%, as estimated in [33].
The visibility of the Ar 425.9nm emission peak plays an
important role in Te determination in our case, whereas the
750.4nm Ar peak always has a high intensity. The high-res
olution spectra of the 425.9nm peak are given in figure6. As
we can see, in spite of the presence of the metallic emission
peaks in the vicinity of Ar peak, the overlap is rather small
[46]. In the case of the Ag target, the side Ag I emission lines
result in the broadening of the resulting spectral line, and at the
same time do not influence its amplitude significantly. Another
important parameter for Te determination, namely the Ar 1s5
state density, is taken to be equal to ~1010 cm3 at 20 mTorr
of working pressure, based on the separate optical absorption
measurements performed in the ArTi HiPIMS discharge under
our discharge conditions (at the end of the plasma pulse, 5cm
above the target). Since expression (11) is weakly sensitive to
7
N Britun etal
Figure 7. The electron temperature determined at the end of the
HiPIMS discharge pulse (50 s) using the Ar line ratio method
[33] as a function of (a) O2 flow fraction (at 15 mTorr) and (b) Ar
pressure (at 40% O2). EP=0.5 J.
the pressure-induced changes of the Ar 1s5 state population in
the studied pressure range, this dependence is neglected.
The Te values determined in our case are given in figure7.
As we can see, Te does not change much as a result of O2 addi
tion, decreasing slightly as the working pressure increases.
The last observation correlates well with the general elec
tron temperature behavior in a glow discharge obtained
by Sato [47]. Since all the estimated Te values are grouped
around 2eV, this value is taken for calculation of the elec
tron excitation coefficients. If necessary, for a broader range
of plasma conditions, when Te changes considerably, further
corrections can be made, based on figure4(a). The obtained
Te values correlate with those measured in a HiPIMS dis
charge during the plasma pulse [34], as well as right after the
plasma pulse [41].
4.2. Time-resolved discharge evolution
Figure 8 represents the time evolution of the 2D distributions
corresponding to the excited species at the beginning of the
plasma afterglow for three target materials. In this case, the
emission signal is mainly represented by the excited Ar (2p3
and 2p8 states), with a small (<10%) contribution from the
excited O. As we can see, at the beginning of the afterglow
the excited species are concentrated in the racetrack vicinity,
and they then propagate upwards in the form of a merged
wave. These results correlate very well with the time-resolved
behavior of Ti ground state ions in the HiPIMS afterglow [17],
as well as the OES imaging results obtained by Hala etal [13].
The TALIF signal from the atomic ground state oxygen (rep
resented by a bright horizontal line) only becomes visible at
J. Phys. D: Appl. Phys. 50 (2017) 075204
Figure 8. The OES mapping corresponding to the Ar 2p3 and 2p8
excited states (O emission contribution is<10%) measured through
an optical 840nm (10nm wide) bandpass filter after the HiPIMS
pulse. The time delays are indicated in the corners. The bright
horizontal line corresponds to the O TALIF signal. Pressure=15
mTorr, O2 flow fraction=40% and EP=0.5 J.
about 6570 s, i.e. 20 s after the plasma pulse. It is much
weaker in the Ti case. The TALIF signal increases gradually
during the off-time, being horizontally uniform, which is dif
ferent from the spatial distributions obtained for Ar metasta
bles and Ti ground state ions in HiPIMS [17]. At the same
time, the appearance of an O TALIF signal corroborates the
spatial distribution of the sputtered neutrals arriving during
this time to the volume of interest [17], implying that some
part of the O atoms is obtained from dissociation of the sput
tered compounds, as suggested in [38]. In addition, direct
sputtering of the O atoms from the poisoned target surface
might also lead to the measured increase in O atom density, as
suggested in [19, 48].
A detailed time evolution of the O density in the plasma
off-time measured for different target materials is given in
figure9. In spite of the fact that the plasma afterglow emission
affects the TALIF signal detection strongly at the beginning
of the off-time, the general increase in O ground state density
after the HiPIMS pulse is clearly visible (it is less pronounced
N Britun etal
Figure 9. The evolution of the O TALIF signal after the HiPIMS
pulse for different target materials. Ar pressure=15 mTorr, O2 flow
fraction=40% and EP=0.5 J.
for Ag, though), confirming the presence of the O atom wave
after the plasma pulse, similarly to the Ti neutrals [17, 37]. In
addition, the data presented in figure9 allow us to displace the
OES and TALIF measurement points for the sake of O atom
density calibration (shown by arrows) in order to avoid strong
afterglow emission preventing reliable TALIF signal detection
at low laser power.
4.3. O atom number density
4.3.1.O2 admixture effect. The O atom number densities
measured by emission actinometry as a function of O2 flow
fraction in the gas mixture are shown in figure10. In this case,
the Ar emission lines listed in table3 were used (except for the
750.4nm peak, which was excluded from the consideration to
reduce data dispersion). The measurements were performed at
15 mTorr of working pressure at the end of the plasma pulse
(50 s). The influence of Ar metastables is neglected in this
case, since it might only increase the obtained densities by a
factor of about 1.2 (see table3). The errors bars shown cor
respond to the standard deviation of the values obtained by
different Ar spectral peaks.
As one can see from figure10, the measured O atom den
sity increases proportionally to the O2 flow fraction, showing
comparable values for Ag, Cu and W targets. In the case of
the Ti target, however, the O number density values are sev
eral times smaller. The relative O density values measured by
TALIF are also given (see figure10(e)), showing rather good
correlation with the OES data. The TALIF data points are nor
malized to the 50 s time delay in this case, using the trends
shown in figure9. The total change of the O TALIF signal in
the W case is much smaller than that measured by OES, which
remains unclear and requires additional experimental verifica
tion. The values obtained at an O2 flow fraction of 40% were
taken as the reference values for TALIF signal calibration for
the further results.
Assuming that electron impact is the main mechanism for
O2 dissociation, the production of O atoms as a result of this
process (O2 + e O + O) should be comparable for the con
sidered targets, as the ISEE coefficients in the poisoned mode
are roughly comparable for these materials [49, 50]. At the
8
J. Phys. D: Appl. Phys. 50 (2017) 075204
Figure 10. O ground state density determined using the OES
(a)(d) and TALIF (e) techniques as a function of the O2 flow
fraction in the ArO2 mixture. The TALIF data are renormalized
to a 50 s delay time, according to figure9. Ar pressure=15 mTorr
and EP=0.5 J.
same time, the fact that the O TALIF signal obtained with a Ti
target is comparable to that of the other targets (figure 10(e)),
whereas the O number density found by OES is several times
lower in the Ti case, deserves special attention. This effect
might be related to Tis significantly higher getter rate, which is
known from the literature [51]. Sputtered Ti (or Ti-based com
pounds) may also chemisorb reactive gases (O in our case) in
the discharge volume [52], even though this process seems to
be less probable, taking into account the low Ti densities in the
poisoned mode ([Ti]<1011 cm3 versus [O]>1012 cm3).
While the gettering of O2 by the Ti target should reduce O pro
duction in the discharge volume, the O-containing compounds
N Britun etal
sputtered and dissociated by electron impact should be the
main source of O (TiO + e Ti + O) in this case. As a result
of gettering, the OES measurements show a reduced value
of O oxygen in the discharge volume. On the other hand, in
the presence of a laser, photodissociation may be a decisive
factor for detaching O from Ti compounds (clusters, etc).
This may elevate the O atom quantity in the laser-probed
volume and increase the resulting TALIF signal (according
to XO + h las X + O, where XO detones the sputtered
compounds, accompanied by O + 2h las O O + hfluor).
The photodissociation of the O2 molecules that dominate in
the discharge ([O2] ~ 1014 cm3), at the same time, should
be comparable for all targets, and negligible, according to the
estimates of Li etal [53]. The lack of photodissociation cross-
section data for Ti-based (as well as other compounds) does
not allow us to verify this hypothesis, however. Joint exper
imental and modeling studies that take into account the effects
of gettering and compound sputtering, their photoionization,
and other relevant mechanisms, should clarify this issue.
The dissociation degree of the molecular oxygen in the
1
discharge volume is defined as 2 [O] / [O2], where [] denotes
the ground state number density. According to our measure
ments, at the point of interest (z5cm) the dissociation
degree does not depend much on the O2 flow fraction and is
estimated to be ~2030% for Ag, Cu and W, and only about
6% for Ti. This should be related to the general stability of
the electron temperature for these conditions, as shown in
figure7(a). It should be noted, however, that O2 density in our
case is determined based on the global pressure, neglecting
the gettering effect, which may introduce a systematic error
into the determined dissociation degree. The precise dissocia
tion degree of O2 can only be obtained by applying local O2
density measurements.
4.3.2.Pressure effect. The O number density as a func
tion of the gas pressure (for the Ar40% O2 gas mixture) is
given in figure11. A rather good correlation between the OES
(figures 11(a)(c)) and TALIF (figure 11(d)) data is obtained.
The O density increases proportionally to the gas pressure, dem
onstrating a total jump of about 1.5 orders of magnitude. The
O density values for Ti target are lower, as in the previous case.
The degree of O2 dissociation in this case changes by a
factor of nearly two with the increase of the gas pressure from
3 to 20 mTorr, as shown in figure12. The obtained dissocia
tion degrees for Ar and Cu are very close, ranging between
20 and 40%. In the case of Ti, this parameter, as expected, is
about threefour times lower, correlating with the data shown
previously.
4.3.3. Gas flow and power effects. Another effect is observed
under the change of the total gas flow, while the gas pressure
is kept constant (15 mTorr in this case). As shown in figure13,
the O atom density increases by a factor of about four (for
Ag) and about two (for Ti) as a result of the gas flow increase
from 10 to 80sccm. These effects also correlate well with the
TALIF measurements of the O atom density (data not shown
here).
9
J. Phys. D: Appl. Phys. 50 (2017) 075204 N Britun etal

Figure 12. The O2 dissociation degree 5cm above the target

calculated at the end of the plasma pulse (50 s) based on the data
from figure11. O2 flow fraction=40% and EP=0.5 J.

Figure 11. O ground state density determined using the OES

(a)(c) and TALIF (d) techniques as a function of the total gas
pressure. The TALIF data are renormalized to a 50 s delay time
according to figure9. O2 flow fraction=40% and EP=0.5 J.

Interestingly, the measured O ground state density

remains weakly sensitive to the discharge power (or pulse
energy EP). As shown in figure14, where the O atom density
is given as a function of EP, the production of ground state
atomic oxygen increases by a factor of ~1.5 during a nearly
fivefold increase of the pulse energy. This effect is rather
surprising, taking into account the direct proportionality of
the sputtered material to the pulse energy in HiPIMS [17].
This phenomenon might be explained by the competition of
the sputtering and the recombination of O atoms with the Figure 13. O ground state density determined by OES for
growing amount of sputtering material (atoms, molecules (a) Ag and (b) Ti targets as a function of total gas flow. O2 flow
and clusters) at the elevated pulse energies. This effect can fraction=40%, pressure=15 mTorr and EP=0.5 J.
be clarified in the future, based on modeling studies that
take O production and O recombination rates carefully into the OES-based calibration of the number density is realized at
account. the end of the plasma pulse, as mentioned earlier.
The results of the time- and space-resolved measurements
4.3.4. Time-resolved and spatial effects. The main advantage of the O ground state density in the HiPIMS afterglow are
of the laser-based detection of O atoms in the discharge is the presented in figure 15. The measurements are performed
ability to measure this quantity during the plasma afterglow, for four target materials at an O2 flow fraction of 40%. The
which is especially important in the HiPIMS case. In our case, measurement errors of in this case are determined by density

10
J. Phys. D: Appl. Phys. 50 (2017) 075204 N Britun etal

Figure 14. The variations of the O TALIF signal as a function of

the pulse energy EP for two target materials. Pressure=20 mTorr
and O2 flow fraction=40%. The delay times are 100 s (W) and
300 s (Cu).

calibration and are similar to those shown in figures10 and 11.

In figure15 the total range of the O number density covers
nearly three orders of magnitude, starting at about 5 1014 cm3
at the very beginning of the plasma off-time before it
decays rapidly down to the detection limit at the end of
the off-time, when the TALIF signal is comparable to the
detector noise (~1012 cm3). As in the previous cases, the
dynamics of the O density is comparable for all the target
materials, with somewhat lower densities corresponding
to the Ti case, as observed previously. It should be noted
that the O atom density values we obtained from the target
surface for Ti at z=25mm (see figure 15), when recal
culated to an O2 flow fraction of 5% (~1013 cm3), are in
good agreement with the modeling results obtained in the
HiPIMS ionization region at the end of the pulse at a com
parable pulse energy [48].
For each target material, the O density distributions are
already merged (or equilibrated) after about 200 s, showing
rather close density values and nearly the same behavior,
nearly independent of the distance. At short time delays, how
ever, the O density depends strongly on the distance from the
target, changing by a factor of about ten (for Ti and Cu) when
the values found at z=65mm and at z=25mm are com
pared. The propagation of the wave of neutral O atoms is also
visible in the case of Cu and W (shown by arrows). A rough
estimate of the velocity of this wave gives a value of ~1 km
Figure 15.(a)(d) The time- and space-resolved O ground state
s1, which is comparable to the typical velocity of sputtered density determined for different target materials in the HiPIMS
atoms found for similar conditions in HiPIMS by LIF [17] and afterglow. The distance z from the target surface is indicated on the
OES [13], and also to the values found in DCMS [15]. legend. (e) The magnified view of the W case. The arrows indicate
Interestingly, in all cases, the temporal evolution of the the O density peaks observed at selected distances. Pressure=
O atom density reveals a weakly pronounced peak at a time 15 mTorr, O2 flow fraction=40% and EP=0.5 J. the vertical
dashed lines mark the end of the plasma pulse.
delay of about 500 s. Its appearance correlates very well
with the refill of Ar metastables in the discharge volume 5.Conclusions
detected in [17]. Due to this observation, we may suggest
the presence of a small (but decent) contribution of Ar meta In this work, the O ground state atom density is determined
stables to the O dissociation process in the bulk of HiPIMS in a short-pulse (50 s) reactive HiPIMS discharge using a
afterglow (O2 + Ar met O + O), together with Armet -assisted combination of optical emission spectroscopy and laser-
creation of the O metastable states (Ar met + O O met + Ar), induced fluorescence techniques. In addition to the calibration
as suggested elsewhere [19, 40]. The contribution of Armet to of O atom density by emission actinometry, a method (called
O2 dissociation during the plasma on-time should be much absorption actinometry) based on the ratio of O and Ar meta
more essential, causing the large difference in the Armet den stable state populations is proposed. These two calibration
sity measured during the plasma on-time and off-time [37]. methods give comparable results.

11
J. Phys. D: Appl. Phys. 50 (2017) 075204
The effects of O2 admixture, gas pressure and applied
power on O atom number density are studied, and generally
show good agreement between the OES and TALIF data. The
O number density in the discharge afterglow ranges between
~1012 cm3 and ~5 1014 cm3, depending on the time delay
in the afterglow and the distance to the target. The O atom
density is found to be weakly sensitive to the applied power.
In addition, the O atom density in the case of the Ti target
appears to be several times lower than in the other examined
cases (Ag, Cu and W). Further experiments involving the veri
fication of the role of photoionization, as well as different O
density calibration methods, may clarify this point.
Time- and space-resolved measurements show that the O
atom density equilibrates at the time delays above 150 s
after the plasma pulse. At the beginning of the off-time (10
50 s after the plasma pulse) the wave of neutral O atoms
is detected. Its propagation velocity (~1 km s1) is compa
rable to the typical velocity of sputtered atoms in DCMS and
HiPIMS discharges. In addition to this, a faint but clearly vis
ible secondary O density maximum appearing at about 500 s
in the off-time correlates clearly with the refill of the Ar meta
stable atoms in this discharge region (measured previously),
indicating the role of O2 dissociation by metastable species.
It should be also noted that the performed measurements
may contain errors. Some of these relate to the assumptions of
the corona+metastable excitation in the actinometry method
or come from the electron temperature estimates, but the main
source is probably the gas rarefaction above the target. Indeed,
it is suggested that the proposed density calibration comes at
the end of the plasma on-time above the target surface, where
Ar gas can be rarefied. The global Ar pressure measurements
used in this work for Ar density estimation do not take this
effectwhich can only be measured locallyinto account.
However, we think that at the moderate applied power levels
used in this study the effect of Ar rarefaction at 5cm is rather
small. The precision of the proposed quantification techniques
can be further enhanced by e.g. (i) quantification of the gas
rarefaction above the target by laser-based measurements
(with and without discharge) in the calibration point, (ii) pre
cise calculation of the excitation coefficients, (iii) improved
Te determination, including direct probe measurements, (iv)
precise calculation of the role of metastable states in Ar exci
tation, (v) more reliable metastable density detection for
absorption actinometry and (vi) improved signal-background
separation during and after the plasma pulse, etc.
In general, the results of this work establish new ways to
quantify the O ground state density in HiPIMS discharges, which
are in great demand for future research work related to reactive
sputtering. The obtained results can also be used to calculate the
O atom flux on film surfaces, estimate the dissociation degrees of
molecular oxygen in the plasma bulk and model reactive HiPIMS
discharges.
Acknowledgments
This work is supported by the Belgian government through the
Ple dAttraction Interuniversitaire (PAI, P7/34, Plasma
Surface Interaction, ). NB acknowledges the support of the
N Britun etal
REFORGAS GreenWin project (grant no. 7267). AB thanks
the University of West Bohemia in Plze for support under
the projects SGS-2016-056 and INTER-16. TS was partially
supported by the Portuguese FCT, under the projects UID/
FIS/50010/2013 and PTDC/FIS-PLA/1420/2014.
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