Comparison of pulsed dc and rf hollow cathode depositions of Cr and CrN lms

H. Barnkov , L. Brdos
Uppsala University, Angstrom Laboratory, Plasma Group, Box 534, SE-751 21 Uppsala, Sweden
a b s t r a c t a r t i c l e i n f o
Article history:
Received 8 November 2010
Accepted in revised form 3 March 2011
Available online 12 March 2011
Keywords:
Diffuse arc deposition
Pulsed dc hollow cathode
Radio frequency hollow cathode
Chromium nitride (CrN)
Chromium (Cr)
A cylindrical chromium hollow cathode powered by a pulsed dc generator working in a constant power mode
was used for PVD of chromium and chromium nitride lms on silicon substrates in argon and nitrogen
plasmas, respectively. A comparison of the pulsed dc process with the radio frequency hollow cathode
depositions of Cr and CrN lms at identical power levels shows considerable differences particularly in the
deposition rate of Cr lms. At the pulsed power above 250 W the hot cathode/diffuse arc regimes were
reached with the cathode outlet temperature as high as 1300 C and the maximumdeposition rates of both Cr
and CrNlms exceeded 1 m/min. The resulting lmproperties, e.g. the microstructure and morphology were
studied and compared with the lms obtained by the rf hollow cathode PVD.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The more stringent environmental legislation initiated large-scale
replacements of chromium electroplating technology by alternative
methods, among which the Physical Vapor Deposition (PVD)
represents the most prospective one. However, besides the lm
quality, a sufciently high deposition rate comparable with electro-
plating is a challenge. Recently the radio frequency (rf) hollow
cathodes made from Cr were successfully tested in the diffuse arc
modes for high-rate depositions of Cr and CrN lms [13]. In those
experiments the Hollow Cathode Plasma Jet (HCPJ) system was
powered by a 13.56 MHz generator. At powers above 200 W the Cr
cathode outlet was heated up to the temperatures over 1300 C which
resulted in very high deposition rates of lms in the jet axis belowthe
cathode on unheated silicon or steel substrates. The rates up to about
1 m/min were obtained for the Cr lm deposition in the Ar plasma
and even higher rates, exceeding 2.5 m/min were achieved for the
CrN lm depositions in N
2
plasmas. Even though the hollow cathodes
have already been used indirectly to enhance deposition of Cr and CrN
lms using the Activated Reactive Evaporation [4,5], as to our
knowledge there have been no other attempts yet to use the Cr
hollow cathodes directly as a target either for non-reactive or for
reactive PVD of Cr based lms.
A motivation for the present work was to test the pulsed dc
deposition in the same hollow cathode system, because the pulsed dc
power might be considered as a technically more feasible alternative
to the rf power. Several successful attempts with the pulsed power
have already been reported in depositions of CrN lms, e.g. the pulsed
dc magnetron sputtering [6], pulsed laser ablation [7], or the high
power impulse magnetron sputtering [8]. Comparative studies, e.g. of
dc and pulsed dc magnetron sputtering depositions [9] or of
superimposing the pulsed signal over the dc or rf power [10], have
been presented, too. The rst results on pulsed dc Hollow Cathode
Plasma Jet (HCPJ) depositions of Cr and CrN were published in [11]. In
this paper we compare the pulsed dc power generation with the rf
generation in the HCPJ systemat the same average power delivered to
the plasma and discuss similarities and differences in the PVD
processes as well as comparison of the lm properties in both the
non-reactive depositions of the Cr lms in argon plasma and the
reactive deposition in pure nitrogen plasma.
2. Experimental arrangement
A cylindrical hollow cathode (outer diameter of 6 mm, internal
diameter of 2.5 mm) fromchromiumpowered by pulsed dc generator
was used for PVD of Cr and CrN lms. A schematic diagram of the
experimental setup is shown in Fig. 1. The generator (ENI, RPG-50)
was operated in a constant power mode in the interval between 150
and 350 W at 250 kHz with 500 ns pulses. The CrN lms were
deposited in pure nitrogen and the Cr lms in pure argon, both at gas
pressures of 67 Pa (0.5 Torr) in the chamber. The target-to-substrate
distance was 10 mm. The lms were deposited on unheated silicon
substrates placed on a thermally insulated sample holder with a
thermocouple temperature sensor. The maximum temperature at the
substrate heated by the plasma itself during the deposition process
did not exceed 350 C. Note that the pulsed dc plasma regimes led to
about 50 C lower substrate temperatures than those in the rf plasma
at comparable power [1]. The temperature of the cathode outlet wall
was measured by an infrared thermometer M90H (Mikron Instru-
ments Co).
Surface & Coatings Technology 205 (2011) 41694176
Corresponding author.
E-mail address: hana.barankova@angstrom.uu.se (H. Barnkov).
0257-8972/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2011.03.013
Contents lists available at ScienceDirect
Surface & Coatings Technology
j our nal homepage: www. el sevi er. com/ l ocat e/ sur f coat
The thickness of lms was measured by a Veeco Dektak V 200-stylus
proler and/or determined by scanning electron microscopy (SEM) on
fracture cross-sections. The morphology and microcrystalline structure
of the Cr and CrN lms deposited at different powers were studied in
details on SEM images taken from both the lm surfaces and fracture
cross-sections, as well as by the X-Ray Diffraction (XRD). The lm
nanohardness was measured by a XP Nanoindenter with Berkovich
tip at loads between 3 and 5 mN.
3. Results and discussion
3.1. Film deposition rates
Fig. 2 shows the Cr hollow cathode temperatures measured 7 mm
above the cathode outlet versus power. The measurements are takenfor
both pulsed dc and rf regimes, in Ar and N
2
plasmas. The highest values
are observed for the Ar plasma in the pulsed dc mode. The voltages are
high (several hundred V) in the pulsed dc regime and especially in
combination with a high secondary electron emission coefcient for Ar,
the ion bombardment leads to very high temperatures. At 150 W the
hollow cathode plasma had a tendency of arcing and the temperature
Fig. 1. Experimental arrangement with the cylindrical Cr hollow cathode powered from the pulsed dc generator. The photograph is taken from the Ar Hollow Cathode Plasma Jet
(HCPJ) discharge at 300 W.
0
500
1000
1500
0 50 100 150 200 250 300 350 400
C
a
t
h
o
d
e

t
e
m
p
e
r
a
t
u
r
e

[

C
]
Power [W]
Ar
Ar
N
2
N
2
Pulsed DC
RF
arcing
Fig. 2. Comparison of the Cr hollow cathode wall temperatures 7 mm above the HCPJ
outlet in pulsed dc and rf power regimes in argon and nitrogen plasmas.
0
500
1000
1500
2000
2500
3000
0 50 100 150 200 250 300 350 400
Pulsed DC
F
i
l
m

g
r
o
w
t
h

r
a
t
e


[
n
m
/
m
i
n
]
Power [W]
Cr
CrN CrN
Cr
RF
arc
glow
Fig. 3. The maximum PVD rates of Cr and CrN lms versus power in the pulsed dc and rf
Hollow Cathode Plasma Jets (HCPJ).
4170 H. Barnkov, L. Brdos / Surface & Coatings Technology 205 (2011) 41694176
Fig. 4. SEM micrographs of the Cr lms deposited on Si at different pulsed dc powers. Data are shown on the lm thickness and the PVD time for each layer.
Fig. 5. SEMmicrographs of the fracture cross-sections of the Cr lms deposited on Si at different pulsed dc powers. The scale bars and the time of the PVD process are given for each lm.
4171 H. Barnkov, L. Brdos / Surface & Coatings Technology 205 (2011) 41694176
almost approached the melting point for Cr (1857 C). We have no
explanation yet of these anomalous regimes. We speculate that the
effect might be connected with nitrogen adsorbed at the cathode walls
(either from atmospheric air or from the nitrogen experiments) and
with its strongly exothermic reactions with Ar metastables, see [12].
Also, in this regime, pulsed dc mode in Ar, the distributions of
temperature values from the tip of the Cr cathode along the cathode
length towards the electrode holder indicate that the temperature is
highest inthe distance of about 10 mmfromthe outlet. For the rf hollow
cathodes and also for pulsed dc regimes in the nitrogen plasma the
region of the maximum temperature is several mm closer to the outlet
[11].
In the rf regime the space charge sheaths are formed inside the
hollow cathode; the self-bias voltage across the space-charge sheath
andthe space-charge sheaththickness dependonthegas. The measured
voltages and electric elds are higher for N
2
than in Ar (see e.g. [13]),
which leads to more efcient ion bombardment and higher tempera-
tures at the cathode in the N
2
plasma.
The maximumdepositionrates (in the axis of the hollowcathode) of
the Cr and CrN lms as functions of the power in the pulsed dc and rf
regimes, respectively, are shown in Fig. 3. It is seen that in the pulsed dc
regime the deposition rates of Cr lms are higher than the deposition
rates of the CrN lms at powers below 300 W, i.e. approximately in the
same power region where the Cr cathode temperature in the Ar plasma
exceeds the cathode temperature in the N
2
plasma and where the
release of Cr by controlled evaporation is more efcient. For the rf
generation, the CrN deposition rate was always higher than the Cr
deposition rate, following the evolution of cathode temperatures [11].
It is also seen that at the same power the rf deposition rates of CrN
lms are higher than those in the pulsed dc regime, while the Cr lms
are deposited substantially faster in the pulsed dc regime. The
difference in Cr (in Ar) deposition rates can be attributed to the
temperature difference at the Cr cathode, while for CrN (in N
2
) the
temperatures are almost the same. It is assumed that in the pulsed
regime (0.5 s on, 3.5 s off) even though the release of Cr is high, the
ionization proceeds only in on part of the pulse and the reactions
between the neutral Cr and N
2
are slower that the reactions between
the ionized species.
The results indicate that the rf powered hollow cathode could be
better for the reactive deposition of CrN lms while the pulsed dc
power can provide higher rates in the non-reactive Cr depositions.
The increased metal content in the alloy lms was reported for the
pulsed dc plasma as compared to the rf regime in [10].
The deposition rates of CrN lms always exceeded 1 m/min in the
diffuse arc regimes where the temperature of the hollow cathode
outlet surpassed 1300 C. This was usually the case for the average
power300 W. An exceptionally high rate, up to almost 3 m/min in
certain cases, has been detected in pulsed dc deposition of Cr lms at
150 W (see Fig. 3).
3.2. Microstructure and morphology of Cr and CrN lms
Cr and CrNlms deposited on Si substrates in the pulsed dc regimes
were studied by SEM and compared with the lms deposited in the rf
regimes. SEM images of the Cr lms deposited at different pulsed dc
powers are shown in Fig. 4. A brous crystalline microstructure of the
Fig. 6. Comparison of Cr lms deposited in the pulsed dc plasma and the rf plasma regimes at 150 W and 300 W.
4172 H. Barnkov, L. Brdos / Surface & Coatings Technology 205 (2011) 41694176
pulsed dc deposited Cr lms is seen in images of the cross-sectional
micrographs in Fig. 5. At highest powers the Cr bers have submicron
widths. The arc based regimes in the argon pulsed dc hollow cathode
plasma led to thick lms (300 m/80 min) with a characteristic
feature of the increasing grain widths with the growing lm thickness.
It is interesting to note that featureless Cr lms grown in the rf
hollow cathode plasma in Ar have a very dense crystalline structure
comparable to the monocrystalline lms. However, their growth rates
are much lower than in the pulsed dc plasma (see Fig. 3). A
comparison of the Cr lms grown at 150 W and 300 W in the pulsed
dc plasma and the rf plasma respectively is shown in Fig. 6. These
results show that the generation mode considerably affects both the
growth rate and the morphology of Cr lms.
The SEM micrographs of the CrN lms deposited by the reactive
PVD in the nitrogen hollow cathode plasma at different pulsed dc
powers are shown in Fig. 7. The thinner lms (below 10 m) are ne-
grained and smooth. This is similar to the growth of CrN lms in the rf
hollow cathode plasma. For comparison the surface of a CrN lm
grown in the rf plasma at 250 W is shown in Fig. 7, too. The lm
morphology at different pulsed dc powers can be seen on SEM images
of the fracture cross-sections in Fig. 8. The last image in the set in Fig. 8
is the cross-section of the CrN lm grown in the rf plasma. The CrN
lms grown in the reactive regimes can also be described as brous up
to 250 W and columnar above this power.
3.3. Crystalline structure of Cr and CrN lms
Similarly as for the Cr and CrN lms deposited by the rf hollow
cathode plasma PVD [13] the XRD analyses conrmed that all Cr and
CrN lms deposited by the hollow cathode plasma PVD in the pulsed
dc regime are crystalline. However, both the main orientation of
Fig. 7. SEMmicrographs of the CrN lms deposited on Si at different pulsed dc powers. The lmthickness is shown in parenthesis for each individual surface. The rf plasma deposited
CrN lm grown at 250 W is given for the comparison.
4173 H. Barnkov, L. Brdos / Surface & Coatings Technology 205 (2011) 41694176
crystals and the texture coefcients of lms are dependent on the
power level as well as on the power regime.
A comparison of the XRD diagrams acquired from Cr lms
deposited at two different powers in the pulsed dc plasma and the
rf plasma, respectively, is shown in Fig. 9. The main feature in all lms
is Cr (110). The Cr lms deposited in the low power (150 W and
200 W) pulsed dc regimes also exhibit peak (211) at about 81.5 (not
shown). This reection disappears at higher power deposited lms.
A comparison of the XRD diagrams fromCrN lms deposited in the
pulsed dc and rf plasmas is shown in Fig. 10. CrN deposited at the high
power (350 W) in the pulsed dc regime is characterized by
preferential orientation (111). With decreasing power, at 250 W,
CrN (200) becomes more prominent. For the rf HCPJ, CrN (111) is
prominent for both, 300 and 250 W. This is connected with the
deposition rate versus power curves. In the rf regime both 300 and
250 W correspond to very high deposition rates, while in the pulsed
dc regime the deposition rate at 250 W is much lower. Thus, the high
deposition rates are linked to (111) preferential orientation, see also
our previous work on the rf hollow cathode plasma [3].
3.4. Mechanical properties of Cr and CrN lms
A comparison of nanoindentation hardness and Young's modulus of
Cr and CrN lms deposited at different powers in pulsed dc plasma and
in the rf plasma is summarized in Table 1. Typical values reported in the
literature, shown in Table 1 relate to the microhardness of lms. For arc
evaporated Cr lms values between 8 and 16 GPa were reported [14].
For dc pulse sputtered CrN lms [6], arc evaporated CrN lms [15] and
arc ion-plated CrN lms [16] the reported microhardness is in the
interval between 16 GPa and 31 GPa. The nanoindentation hardness of
Fig. 8. SEM images of the fracture cross-sections of the CrN lms deposited on Si at different pulsed dc powers. The time of the PVD process is given for each individual lm. The rf
plasma deposited CrN lm grown at 250 W is given for the comparison.
4174 H. Barnkov, L. Brdos / Surface & Coatings Technology 205 (2011) 41694176
CrNlms producedby the magnetron and HIPIMS sputterings ts to the
same interval as well [17]. Note that the pulsed dc plasma deposited Cr
lms exhibit somewhat lower nanoindentation hardness as well as
lower Young's modulus than the rf plasma deposited lms. This might
be connected with their brous microstructures. The CrN lms
deposited in the dc pulsed and rf plasma regimes exhibit comparable
properties.
4. Conclusions
The pulsed dc power has been proven to be an interesting and
prospective alternative to the rf plasma in the hollow cathode plasma
PVD of Cr and CrN lms. However, considerable differences have been
found between the pulsed dc and rf hollowcathode plasma regimes in
both the PVD rates and in properties of the deposited lms. These
differences can be very important for selection of power generator for
required lm applications.
The lm deposition rates always exceed 1 m/min in the diffuse
arc regimes where the temperature of the hollow cathode outlet
surpasses 1300 C. An exceptionally high rate, up to almost 3 m/min
in certain cases, has been detected in the pulsed dc deposition of Cr
lms in argon plasma at 150 W. This was accompanied by an
enhanced temperature of the cathode outlet and a cavity-shaped
erosion inside the cathode. The reason for this effect is not understood
yet.
Heating of the substrate by the pulsed dc plasma is lower than by
the rf plasma, resulting in about 50 C lower temperature. This fact is
important for PVD of lms on temperature sensitive substrates.
The pulsed dc plasma enhances the PVD of Cr lms and causes a
brous crystalline microstructure, while the rf plasma enhances the
reactive PVD of CrN lms.
Cr lms deposited both in the pulsed dc and in the rf regimes
exhibit dominant (110) orientation. CrN lms deposited at very high
deposition rates (above 1 m/min) exhibit (111) preferential orien-
tation, both for the pulsed dc and rf hollow cathode plasmas. Lower
deposition rates lead to CrN (200) being more prominent.
The Cr lms deposited in the pulsed dc plasma exhibit somewhat
lower nanoindentation hardness as well as lower Young's modulus
than the Cr lms deposited by the rf plasma. The CrN lms deposited
in both kinds of power regimes exhibit comparable properties.
It is evident that due to exceptionally high PVD rates of Cr and CrN
lms achieved in the hollowcathode plasma systems in the diffuse arc
modes for both power regimes, as well as due to superior properties of
the lms, the hollow cathode plasma technology represents a very
promising system for the industrial replacement of conventional
electroplating.
0
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
40 45 50 55 60 65 70
I
n
t
e
n
s
i
t
y


[
C
o
u
n
t
s
]
2 theta []
C
r

(
1
1
0
)
300W
150W
C
r

(
2
0
0
)
300W
150W
Pulsed DC
RF
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
I
n
t
e
n
s
i
t
y


[
C
o
u
n
t
s
]
0
Fig. 9. Comparison of the XRD diagrams acquired from Cr lms grown on silicon in the
pulsed dc HCPJ and in the rf HCPJ. The full line curves represent 300 W, the dotted line
curves represent 150 W.
C
r
N

(
1
1
1
)
C
r
N

(
2
0
0
)
C
r
N

(
2
2
0
)
350W
250W
250W
300W
C
r
N

(
2
0
0
)
C
r
N

(
2
2
0
)
0
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
40 45 50 55 60 65 35
I
n
t
e
n
s
i
t
y


[
C
o
u
n
t
s
]
2 theta []
1 10
4
2 10
4
3 10
4
4 10
4
5 10
4
I
n
t
e
n
s
i
t
y


[
C
o
u
n
t
s
]
0
Pulsed DC
RF
Fig. 10. Comparison of the XRD diagrams of CrN lms grown on silicon in the pulsed dc
HCPJ and in the rf HCPJ. The full line curves represent 350 (300) W, the dotted line
curves represent 250 W.
Table 1
Comparison of typical values of the nanoindentation hardness and the Young's modulus
measured for Cr and CrN lms deposited in the pulsed dc HCPJ and in the rf HCPJ at
different powers delivered into the plasma.
Film and PVD
power regime
Power
[W]
Deposition
time [min]
Film
thickness
(max) [m]
Nanoindent.
hardness
[GPa]
Young's
modulus
[GPa]
Cr pulsed dc 300 10 11 45 120140
CrN pulsed dc 150 100 4.2 1923 180230
CrN pulsed dc 250 30 4 1722 200290
Cr rf 300 10 2.9 1315 249
CrN rf 250 20 35 23 278
Typical values reported: Cr 816
CrN 1631
4175 H. Barnkov, L. Brdos / Surface & Coatings Technology 205 (2011) 41694176
Acknowledgements
Financial supports from the Foundation for Strategic Environmen-
tal Research (MISTRA) and from the Johan Gustaf Richerts Scientic
Foundation in Sweden are gratefully acknowledged. The authors are
thankful to Dr. Lars-Erik Gustavsson from the Plasma Group for the
SEM images and for XRD measurements of lms.
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