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A comparison of the oxidation behavior of CrN lms deposited using continuous dc,

pulsed dc and modulated pulsed power magnetron sputtering


Jianliang Lin
a,
, Ningyi Zhang
a
, William D. Sproul
a, b
, John J. Moore
a
a
Advanced Coatings and Surface Engineering Laboratory (ACSEL), Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, CO, 80401, USA
b
Reactive Sputtering, Inc, 2152 Goya Place, San Marcos, CA, 92078 USA
a b s t r a c t a r t i c l e i n f o
Article history:
Received 3 June 2011
Accepted in revised form 16 January 2012
Available online 26 January 2012
Keywords:
CrN lms
Modulated pulsed power (MPP) magnetron
sputtering
High power pulse magnetron sputtering
(HPPMS)
High power impulse power magnetron
sputtering (HIPIMS)
Oxidation
Activation energy
The study is aimed at comparing the oxidation behavior of the stoichiometric CrN lms deposited by contin-
uous dc magnetron sputtering (dcMS), mid-frequency pulsed dc magnetron sputtering (PMS), and modulat-
ed pulsed power (MPP) magnetron sputtering techniques in a closed eld unbalanced magnetron sputtering
system. These as-deposited CrN lms exhibited a cubic structure and similar stoichiometric compositions, but
with different microstructures and residual stresses. After annealing in the ambient air from 600 to 1000 C,
the changes in the crystal phase, microstructure, and hardness of the lms were characterized using X-ray
diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy line scan, and nanoindenta-
tion. The oxidation activation energies of the lms were calculated using Arrhenius equation. It was found
that the MPP CrN lm exhibited superior oxidation resistance than dcMS and PMS CrN lms. After annealing
at 900 C, the MPP CrN lm exhibited an extremely dense structure and the cubic phase was well maintained.
On the other hand, the dcMS and PMS CrN lms were severely oxidized into a porous structure with the de-
velopment of -Cr
2
N and Cr
2
O
3
phases and a rapid degradation of the cubic phase after 700 and 800 C, re-
spectively. The results indicate that all lms showed a parabolic oxidation rate below 900 C. The oxidation
activation energies for the dcMS, PMS and MPP CrN lms are 116 kJ/mol, 141 kJ/mol, and 195 kJ/mol, respec-
tively. The better oxidation resistance of the MPP CrN lm is attributed to its dense microstructure and low
residual stress.
Published by Elsevier B.V.
1. Introduction
As one of the transition metal nitride lms, CrN lms have been
extensively studied for material protection due to their high hard-
ness, good wear resistance, chemical inertness, and good thermal sta-
bility. Magnetron sputtering is a convenient and widely used
technique for CrN lm depositions. The CrN lms have been widely
deposited using continuous dc magnetron sputtering (dcMS) [15],
mid-frequency pulsed dc magnetron sputtering (PMS) [6] and recent-
ly high power pulsed magnetron sputtering (HPPMS) techniques
[7,8]. The oxidation behavior and thermal stability of the CrN lms
deposited by dcMS and PMS have been widely reported [15]. In gen-
eral, the cubic CrN (c-CrN) lm degraded rapidly after 600 C through
the formation of hexagonal Cr
2
N (-Cr
2
N) phase by the outward dif-
fusion of N [9,10]. This process was accompanied by the grain growth
and a decrease in the lm residual stresses and defects (e.g. intersti-
tials and dislocations). The observation of the Cr
2
O
3
formation on
the CrN lm surface was widely reported from 500600 C, which
was dominated by the outward diffusion of Cr and inward diffusion
of O through the formed Cr
2
O
3
layer [11,12]. The oxidation rate was
found to t a parabolic time law.
The oxidation resistance and thermal stability of nanostructured
lms depend on many factors, including the lmchemical composition,
microstructure, residual stress, and defect density formed during the
deposition process. Djouadi et al. [13] have shown that the stoichiomet-
ric c-CrN lms exhibited better oxidation resistance and thermal stabil-
ity than the nitrogen decient -Cr
2
N lms because of the existence of
metallic Cr in the Cr
2
N lms. From a structural point of view, since the
oxidation kinetics of a nanocrystalline lm were dominated by the out-
ward cationic diffusion and inward diffusion of O through the grain
boundaries, the activation energy for the diffusion is largely dependent
on the density, grain boundary, and grain size of the as-deposited lms.
It is not a surprise that the cationic and cathodic diffusions need much
higher activation energies to pass through a dense lmthan in a porous
lm.
In general, the development of compressive residual stresses and
the incorporation of certain levels of defects in the hard lms can ef-
fectively increase the hardness of the lms. However, from a thermo-
dynamic point of view, these high residual stress and defect densities
also result in an intrinsic instability of the microstructure of the lms
at evaluated temperatures. Veprek [14] has pointed out that a num-
ber of superhard lms lost their superhardness whenever such lms
Surface & Coatings Technology 206 (2012) 32833290
Corresponding author. Tel.: +1 303 273 3178; fax: +1 303 273 3795.
E-mail address: jlin@mines.edu (J. Lin).
0257-8972/$ see front matter. Published by Elsevier B.V.
doi:10.1016/j.surfcoat.2012.01.033
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are annealed to a temperature higher than the deposition tempera-
ture due to the relaxation of the compressive stress and defects (e.g.
interstitials and dislocations) originating from the energetic ion bom-
bardment during deposition. Mitterer [15] and Mayrhofer [16] sug-
gested that an introduction of high defect densities to obtain
superhard lms might result in reduced thermal stability because of
the lower thermal activation needed to start recovery in such
structures.
Considering the above factors, one of the effective approaches to
increasing the thermal stability of nanostructured lms is to increase
the density of the lms while reducing the stresses and defects in the
lms by carefully controlling the deposition parameters, e.g. the ion
bombardment energies and ion uxes. Nevertheless, these plasma
conditions strongly depend on the sputtering techniques. In recent
years, HPPMS (also named high power impulse magnetron sputtering
(HIPIMS)) [1720] and its alternative technique modulated pulsed
power (MPP) magnetron sputtering [2124] were developed to gen-
erate a high degree of ionization of the target species by using pulsed
high peak power on the target. It was suggested that the high instan-
taneous deposition rate during the on time of the high power pulse
leads to high initial nucleation island densities, and the intense ion ir-
radiation of the growing lm by the high metal ion ux providing
densication via ion bombardment-induced adatom migration [25].
Ehiasarian et al. [26] improved the structure and wear resistance of
CrN lms deposited by HIPIMS compared with arc bond sputtering.
Recently, Lin et al. [7] also observed improvements in the density, ad-
hesion, mechanical, and tribological properties of CrN lms deposited
by MPP compared with dcMS and PMS without using external bias
and heating. Thick and dense CrN lms (up to 55 m) have been suc-
cessfully deposited at a high deposition rate using the MPP technique
[27].
In comparison with the traditional HPPMS/HIPIMS technique, the
MPP technique has a higher deposition rate [22,28]. The MPP plasma
exhibited large metallic ion uxes. These ions show a major peak ion
energy of 25 eV and a small ion energy tail with the maximum ener-
gy less than 30 eV [7,23]. The large metallic ion ux in the MPP plas-
ma provides enhanced ion bombardment on the growing lm to
achieve a fully dense structure. Nevertheless, the residual stress and
the defect density of the MPP lms can be maintained low because
of the low ion energies of the majority of the ions [7]. As discussed
previously, these factors are critical for the thermal stability of nano-
structured hard lms. Therefore, it is expected that the MPP lms may
exhibit a different oxidation behavior and thermal stability compared
to the lms deposited by traditional magnetron sputtering techniques
(e.g. dcMS and PMS). Although recent research has demonstrated the
improved microstructure, adhesion, mechanical and tribological
properties of several hard coating systems deposited by the HPPMS/
HIPIMS and MPP techniques as compared to the traditional magne-
tron sputtering techniques, no studies have been reported on the
comparison of the oxidation resistance and thermal stability of
these lms.
Therefore, the aim of this study is to use the CrN lm as an exam-
ple to compare the oxidation behavior of the nanostructured lms
deposited by dcMS, PMS, and MPP techniques with a similar stoichi-
ometry and thickness, but with different microstructures and internal
stresses. The CrN lms were annealed from 600 C to 1000 C in the
ambient air. After the oxidation tests, changes in the crystal phase,
microstructure, oxide layer thickness and hardness of the CrN lms
were characterized and compared. The oxidation activation energy
of these CrN lms was obtained using the Arrhenius equation.
2. Experimental details
CrN lms were deposited on AISI 304 stainless steel coupons and
(100) silicon wafers in a closed eld unbalanced magnetron sputter-
ing (CFUBMS) system by reactively sputtering a Cr target
(100 mm300 mm) in an Ar:N
2
mixture. The deposition system is a
cylindrical chamber equipped with two unbalanced magnetrons
(Teer Films, LTD.) of reversed magnetic polarities, which were placed
opposite with a distance of 240 mm to form a closed magnetic eld.
The schematic drawing and detailed descriptions of the CFUBMS sys-
tem can be found in Refs. [24,28]. The substrates were ultrasonically
cleaned in acetone and alcohol for 15 min respectively. The substrates
were installed at about 100 mm away from the Cr target. A base pres-
sure below 1.310
4
Pa was reached prior to all depositions. The
substrates were sputter etched by Ar plasma bombardment at a
1.34 Pa working pressure using a pulsed dc bias of 500 V
(100 kHz and 90% duty cycle) for 30 min.
A thin Cr adhesion layer (100150 nm) was deposited on the sub-
strates. Then the CrN lms were deposited using dcMS (Pinnacle, Ad-
vanced Energy Inc.), PMS (Pinnacle Plus, Advanced Energy Inc.), or
MPP (SOLO/AXIS-180 Pulsed DC Plasma Generator, Zpulser LLC.)
power sources.
Table 1 summarizes the deposition conditions. For the dcMS and
PMS depositions, an average target power (P
a
) of 3 kW was used. In
the PMS depositions, an asymmetric bipolar pulsing voltage was ap-
plied on the Cr target with the pulsing parameters of 100 kHz and
60% duty cycle (the target voltage was reversed to 10% of the nominal
negative sputtering voltage during the positive pulse period). In the
MPP depositions, the pulse length was 1000 s, which contains a
500 s weak ionization stage and a 500 s strong ionization stage
[7]. The peak voltage (V
p
), peak current (I
p
) and peak power (P
p
) on
the target during the strong ionization stage in the pulse were
575 V, 190 A and 95 kW, respectively, whereas P
a
was maintained
constantly at 3 kW. The repetition frequency was 73 Hz, which is re-
lated to the selected P
p
and P
a
. A 50 V DC substrate bias voltage
was applied for all depositions (Axis, Zpulser LLC.). During the depo-
sitions, high purity Ar and N
2
(99.999%) were introduced into the sys-
tem separately using MKS mass ow controllers. The working
pressure, which was measured by a high precision capacitance ma-
nometer, was kept constant at 0.67 Pa. The total gas ow rate was
62 sccm. The N
2
ow rate was maintained at 50% of the total ow
rate.
High temperature oxidation tests were carried out in a CARBOLITE
type 301 furnace. The samples were annealed in an ambient air at el-
evated temperatures from 600 to 1000 C for 1 h. All samples were
Table 1
The deposition conditions for the dcMS, PMS and MPP CrN lms.
Pulsing parameters P
a
[kW] P
p
[kW] I
a
[A] I
p
[A] V
a
[V] V
p
[V] I
d
[A/cm
2
] I
sub
[mA/cm
2
] Pressure [Pa] Ar:N
2
Bias [V]
dcMS N/A 3.0 7.06 425 0.04 1.5 0.67 1:1 50
PMS 100 kHz and 60% duty cycle 3.0 8.92 336 0.05 4.2 0.67 1:1 50
MPP 73 Hz and 7.3% duty cycle 3.0 95 83 190 463 575 1.10 215 0.67 1:1 50
P
a
and P
p
are the average and peak target power.
I
a
and I
p
are the average and peak target current in one pulse length.
V
a
and V
p
are the average and peak target voltage.
I
d
is the peak target current density during the pulse.
I
sub
is the substrate peak ion current density during the pulse.
3284 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290
cooled down to room temperature within the furnace. Special speci-
mens were made by depositing lms on six faces of small pieces of
steel substrates. The weight gain of these lms was measured using
simultaneous thermal analysis (STA) from 600 to 900 C in the ambi-
ent air for 10 h. The thermal ramping to the isothermal oxidation
temperature was set to 40 K min
1
for all samples in a 55 sccmow-
ing Ar atmosphere in order to avoid premature lm oxidation. When
the oxidation isothermal temperature was reached, a ow of air
(30 sccm) was used as the background atmosphere for the ten hour
isothermal test. The oxidation rate constant (k
p
) was obtained from
the weight gain as function of the time of exposure at high tempera-
tures. Then the oxidation activation energy (E
a
) of the lms was cal-
culated by plotting the inverse temperature versus the natural log
of the oxidation rate using the Arrhenius equation.
ln k
p

ln A
E
a
R
1
T
where R is the gas constant, and T is the isothermal temperature.
Then E
a
can be obtained from the slope of the curve.
The crystal structure of the lms was characterized by X-ray dif-
fraction (XRD) using a Siemens diffractometer (Model
KRISTALLOFLEX-810) operated with K

Cu radiation (20 kV and


30 mA) in the conventional BraggBrentano mode. The residual stress
of the lms was measured by glancing incident angle XRD (GIXRD) in
the same X-ray diffractometer. The chemical composition of the as-
deposited lms was investigated by X-ray photoelectron spectrosco-
py (XPS) (PHI model 5600LS) using an Al K

X-ray source. The micro-


structure of the lms was characterized by a eld-emission scanning
electron microscope (SEM) (JSM-7000F) using a 5 kV operation volt-
age. An energy dispersive spectroscopy (EDS) line scan was carried
out along the cross-section of the annealed lms to verify the oxide
layer. The hardness of the lms was measured by a nanoindenter
(NanoIndenter XPTM, MTS Systems Corporation) using a diamond
Berkovich tip. The hardness of the annealed CrN lms was measured
as a function of the indentation depth (up to 500 nm) to distinguish
the hardness of the surface oxide layer and the underlay lm.
3. Results
3.1. Microstructure and properties of the as-deposited CrN lms
Fig. 1 shows the cross-sectional SEM micrographs of the as-
deposited CrN lms. The dcMS CrN lm exhibited a porous columnar
grain structure, which contains long columnar grains and clear grain
boundaries throughout the lm thickness. The fractured morphology
of the dcMS CrN lm indicates an intergranular fracture along the co-
lumnar grains due to the low lm density and weak boundary bond-
ing strength between the grains. The PMS CrN lm showed a dense
microstructure, in which ne granular grains were developed
throughout the lm thickness. In contrast, the MPP CrN lm exhibited
a dense and disordered short columnar grain structure. The bound-
aries between the short columnar grains along the coating thickness
are not as clear as those in the dcMS lm. The laminated features ob-
served from the fractured cross-section of the MPP CrN lm indicate a
transgranular fracture across the crystals due to the high density and
strong boundary bonding strength between the grains [29]. In this
study, the sequence of the deposition rate from high to low is dcMS,
MPP and PMS, which is similar to the results from an earlier study [7].
Fig. 2 shows the XRD patterns of the as-deposited dcMS, PMS and
MPP CrN lms and after annealing at different temperatures. As
shown in Fig. 2, all as-deposited lms exhibit a face centered cubic
(FCC) CrN (c-CrN) structure (circle symbol) (JCPDS 110065). The
dcMS lm shows strong (111) and (200) peaks, and weak (220)
and (311) peaks (Fig. 2A). The PMS lm exhibits a strong (111)
peak and weak (200) and (311) peaks (Fig. 2B). In contrast, the
MPP lm shows a strong (311) peak and weak (111) and (200)
peaks (Fig. 2C). The peaks of the PMS lm shifted to a lower angle
than the dcMS and MPP lms. Since the N/Cr ratios of the lms are
similar, the larger shift of the diffraction peaks in the PMS CrN lm
is attributed to its higher residual stress (Table 2), which was possibly
generated by the high energy ion bombardment from the PMS plas-
ma, which contains a wide range of ion energy distribution for gas
and metal ions (e.g. the maximum ion energy may reach hundreds
of eV) [36]. The grain sizes of the as-deposited dcMS, PMS and MPP
CrN lms were 24.5 nm, 18.9 nm and 14.1 nm respectively, as calcu-
lated using the Scherrer equation [30].
The thickness of the lms varied in a small range of 2.8 to 3.1 m. As
summarized in Table 1, all lms have a near stoichiometric composition
with an N/Cr ratio in the range of 0.94 to 0.98. The Ocontent in the lms
is less than 5 at.%. The compressive residual stresses of the dcMS, PMS,
and MPP CrN lms are 2.0 GPa, 4.5 GPa, and 2.5 GPa, respective-
ly. The hardness and H/E ratio (resistance against elastic strain to fail-
ure) of the dcMS CrN lm are 23 GPa and 0.07, respectively. The PMS
and MPP CrN lms showed similar hardness values of 28 GPa. And
the MPP CrN lm exhibited the highest H/E ratio of 0.087.
Fig. 1. Cross-sectional SEM micrographs of the as-deposited CrN lms deposited using
(A) dcMS, (B) PMS, and (C) MPP techniques.
3285 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290
3.2. Microstructure of the lms after annealing
After annealing at 600 C, the c-CrN peaks of all three lms shifted
toward the standard positions due to the stress and defect relaxations
(for interstitials and dislocations) at elevated temperatures. Strong
diffraction peaks associated with -Cr
2
N phase (down triangle sym-
bol) (JCPDS 350803) and a small amount of Cr
2
O
3
phase (square
symbol) (JCPDS 381479) were detected in the dcMS CrN lm
(Fig. 2A). However, nearly no crystalline oxide diffraction peaks
were detected in the PMS and MPP CrN lms after annealing at
600 C. The XRD patterns of the PMS lm exhibited a strong c-CrN
phase with the appearance of a small amount of -Cr
2
N phase
(Fig. 2B). In contrast, the c-CrN phase was well maintained and al-
most no -Cr
2
N phase was detected in the MPP CrN lm after anneal-
ing at 600 C (Fig. 2C).
The cross-sectional SEM micrographs and the EDS line scan of the
lms after annealing from 700 C to 1000 C are shown from Figs. 3 to
6, respectively.
After annealing at 700 C, the XRD pattern of the dcMS lm
showed dominant -Cr
2
N, Cr
2
O
3
, and weak Cr phases (JCPDS
060694) (diamond label), accompanied with a rapid decrease in
the c-CrN phase (Fig. 2A). The SEM image conrms the grain growth
in the top half of the dcMS lm with the development of a 200 nm
oxide layer on the surface (EDS line scan) (Fig. 3A). For the PMS
CrN lm, the intensity of the -Cr
2
N (110) and (111) peaks increased
signicantly with a rapid decrease in the c-(111) peak after annealing
at 700 C (Fig. 2B). In contrast, only a small amount of -Cr
2
N phase
was formed in the MPP lm (Fig. 2C). As compared to the as-
deposited lms, the increase in the grain size of the PMS and MPP
lms is evident from the SEM images (Fig. 3B and C). The EDS line
scan shows a less than 100 nm thin oxide layer has been formed on
the PMS and MPP lm surface after annealing at 700 C, which can
hardly be seen from the cross-sectional SEM images. However, this
thin oxide layer was conrmed from the XRD patterns, which show
small Cr
2
O
3
(012) and (104) peaks (Fig. 2B and C).
The development of the Cr
2
O
3
phase on the CrN lm surface after
annealing in the air from 600 to 700 C has been mainly explained by
the outward diffusion of Cr species [11,12]. The phase transformation
of the CrN lms from c-CrN to -Cr
2
N upon heat treatment as early
as 500600 C has also been reported [31]. The mechanisms of this
phase transformation have been attributed to the stress relaxation
[31] and outward diffusion of N in the near surface region during
annealing [10]. Therefore, the residual stress level and the density of
the lms play an important role in determining the c-CrN to -Cr
2
N
phase transformation. The relatively low density of the dcMS CrN lm
and the relatively high residual stress in the PMS CrN lm probably
are related to their earlier phase transformation from c-CrN to -Cr
2
N
at elevated temperatures than the dense MPP CrN lm.
After annealing at 800 C, the intensities of the -Cr
2
N and Cr
2
O
3
phases further increased in the dcMS CrN lms, while the c-CrN
phase completely disappeared (Fig. 2A). Similar to the 700 C
annealed PMS lm, the 800 C annealed PMS lm still exhibited a
mixture of the c-CrN and -Cr
2
N phases with a slight increase in the
Cr
2
O
3
peak intensities (Fig. 2B). For the MPP CrN lm, small -Cr
2
N
(110) peak was observed with the disappearance of the c-CrN (111)
peak after 800 C (Fig. 2C). Nevertheless, the MPP CrN lm still
Fig. 2. XRD patterns of the as-deposited (A) dcMS, (B) PMS, and (C) MPP CrN lms and
after annealing at different temperatures (the peaks indexed as S are arisen from the
substrate).
Table 2
The properties and oxidation temperatures for the dcMS, PMS and MPP CrN lms.
Technique N/
Cr
Thickness
[m]
Gain size
(As-dep) [nm]
Residual
stress [GPa]
Hardness,
H [GPa]
Young's
modulus, E [GPa]
H/E Phase formation T
[C]
Stable
T for cubic CrN [C]
-Cr
2
N Cr
2
O
3
dcMS 0.98 2.8 24.5 2.0 23.0 328 0.070 >600 >600 b700
PMS 0.94 2.9 18.9 4.5 27.8 338 0.082 >600 >700 b800
MPP 0.95 3.1 14.1 2.5 28.2 323 0.087 >700 >700 b900
3286 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290
exhibited a strong c-CrN (311) peak, which demonstrated its excel-
lent thermal stability (Fig. 2C). There was a slight increase in the
Cr
2
O
3
peaks of the 800 C annealed MPP CrN lm.
As shown in Fig. 4, a dense Cr
2
O
3
layer was formed and separated
from the underlay large grains by a thin and porous region in the
dcMS and PMS lms after annealing at 800 C. The formation of a po-
rous region under the top dense oxide layer in the CrN lms is mainly
due to the outward diffusion of Cr species to the surface, as widely
reported [11]. As shown in Fig. 4A and B, the top half of the dcMS
and PMS CrN lms exhibited a more porous structure with a larger
grain size than the bottom half of the lms. In contrast, the interface
between the top oxide layer and the MPP lm after annealing at
800 C is dense. Moreover, an extremely dense microstructure
under the top oxide layer can be observed from the MPP CrN lm
after annealing at 800 C (Fig. 4C).
After annealing at 900 C, the intensity of the -Cr
2
N peaks de-
creased signicantly for the dcMS CrN lm, whereas the intensity of
the Cr
2
O
3
peaks increased continuously (Fig. 2A). The c-CrN phase in
the PMS CrN lm disappeared after annealing at 900 C. The PMS CrN
lm also showed a signicant decrease in the -Cr
2
N phase with a fur-
ther increase in the Cr
2
O
3
peaks (Fig. 2B). As shown in Fig. 5A and B, the
SEM images and the EDS line scan conrmed that the dcMS and PMS
CrN lms were severely oxidized after annealing at 900 C. The thick-
ness of the oxide layer on the surface is about 600 nm and 700 nm,
which can be clearly indentied from the SEM images (Fig. 5). The
structure of the dcMS and PMS lms under the top oxide layer became
extremely porous (Fig. 5A and B). The EDS line scan conrms that there
is almost no N content in the surface oxide region, and the N is reduced
in the lms under the oxide layer, especially for the PMS lm. The large
columnar grain boundaries in the dcMS CrN lm possibly lead to the
fast diffusion of N outward from the lms. Although the decreased
grain size favors the improvements in the mechanical properties, the
large inter-crystalline volume fraction (e.g. grain boundaries) in the
PMS CrN lm could also act as outward diffusion paths for N atoms
from thermodynamic point of view.
In contrast, the MPP CrN lm still maintained an excellent oxida-
tion resistance at 900 C. The XRD pattern conrmed that the c-CrN
(311) peak was well maintained after annealing at 900 C (Fig. 2C).
This is further justied by the SEM view of the extremely dense mi-
crostructure developed under the top 600 nm dense oxide layer, as
shown in Fig. 5C. The densication of the MPP CrN lm at elevated
temperatures was mainly attributed to the kinetic growth of the
CrN grains with a decrease in the grain boundary areas by the energy
reduction. Such a dense microstructure in the MPP lm could have a
strong barrier effect for slowing down the outward diffusion of the
Cr and N species and the inward attack from the oxygen. Consequent-
ly, the MPP CrN lm showed excellent phase stability.
As the oxidation temperature reached 1000 C, Fig. 2A shows that
the phases in the dcMS CrN lms are composed of Cr
2
O
3
and Cr, while
the -Cr
2
N phase completely disappeared. The EDS line scan detected
high O content and barely any N content throughout the lm thick-
ness, which indicates the dcMS CrN lm was completely oxidized
(Fig. 6A). The PMS CrN lm was also severely oxidized at 1000 C.
The major phase in the PMS lm was Cr
2
O
3
with a small amount of
Fig. 3. Cross-sectional SEM micrographs and corresponding EDS line scans of (A) dcMS,
(B) PMS, and (C) MPP CrN coatings after annealing at 700 C.
Fig. 4. Cross-sectional SEM micrographs and corresponding EDS line scans of the (A) dcMS,
(B) PMS, and (C) MPP CrN coatings after annealing at 800 C.
3287 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290
-Cr
2
N phase (Fig. 2B). As shown in Fig. 6B, an extremely porous mi-
crostructure was formed under the top fully developed oxide layer.
The thickness of the complete oxidized region in the PMS CrN lm
is about 2 m accompanied with a complete reduction of N in this re-
gion. However, a 1.5 m thick region from the bottom of the PMS lm
exhibited a granular grain structure without O content, which is at-
tributed to the remaining -Cr
2
N in the lm (Fig. 6B).
In contrast, after annealing at 1000 C, the XRD study conrmed
that the MPP CrN lm contained a mixture of -Cr
2
N and Cr
2
O
3
phases (Fig. 2C). The c-CrN phase was completely transferred to -
Cr
2
N phase, which was now the major phase in the lm. The SEM
image and EDS line scan showed that a two layered structure was
formed in the MPP CrN lm, which includes a 1.5 m polycrystalline
Cr
2
O
3
layer and the underlay dense MPP CrN
x
lm(Fig. 6C). The inter-
face between the top oxide layer and the lm became porous. The
EDS line scan showed that N was completely depleted in the top
oxide layer, but it was maintained well in the intact lm. In addition,
no oxygen was detected in the underlay dense lm. These results con-
rmed that the inward diffusion of O and the outward diffusion of Cr
and N were effectively slowed down in the dense MPP CrN lm.
3.3. Mechanical properties
The hardness of the dcMS, PMS and MPP CrN lms was plotted as
a function of the oxidation temperature as shown in Fig. 7. After
annealing at 600 C for 1 h, the hardness of the dcMS, PMS, and
MPP CrN lms dropped down to 18 GPa, 23 GPa and 25 GPa,
respectively. The decrease in the lm hardness is mainly due to the
stress relaxation, annealing of the defects to the grain boundaries,
and also the grain growth. After 600 C, the hardness of all lms de-
creased rapidly as the oxidation temperature was further increased.
The hardness of the dcMS and PMS CrN lms dropped down to 43%
and 45% of the as-deposited hardness after annealing at 800 C.
Fig. 6. Cross-sectional SEM micrographs and corresponding EDS line scans of the (A) dcMS,
(B) PMS, and (C) MPP CrN coatings after annealing at 1000 C.
Fig. 7. Hardness of the dcMS, PMS and MPP CrN lms as a function of the oxidation
temperature.
Fig. 5. Cross-sectional SEM micrographs and corresponding EDS line scans of the (A) dcMS,
(B) PMS, and (C) MPP CrN coatings after annealing at 900 C.
3288 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290
Nevertheless, the MPP CrN lm retained 67% of the as-deposited
hardness after annealing at 800 C.
3.4. Oxidation activation energy
Plots of the square of mass gains per area (m)
2
/cm
4
at different
temperatures for the MPP CrN lms with time are shown in Fig. 8A.
It can be seen that the MPP CrN lms exhibited a parabolic oxidation
rate at the temperature range from 700 C to 900 C. The dcMS and
PMS CrN coatings also exhibited a parabolic oxidation rate (not
shown here). The parabolic oxidation rate constant (k
p
) at each iso-
thermal oxidation temperature (T) was obtained from the slope of
the curves using the equation:
m =cm
2

2
k
p
t:
Fig. 8B shows the Arrhenius plots of ln(k
p
) as a function of 1/T for
dcMS, PMS and MPP CrN lms. The oxidation E
a
obtained from the
slope of plots using the Arrhenius equation for the dcMS, PMS and
MPP CrN lms are 116 kJ/mol, 141 kJ/mol and 195 kJ/mol, respective-
ly. These E
a
values are comparable to the literature reported values for
the CrN lms in a wide range of 98 to 251 kJ/mol [3235].
4. Discussion
The above results have shown that the dcMS, PMS and MPP CrNlms
exhibited different oxidation behaviors in the ambient air. As summa-
rized in Table 2, the MPP CrNlmexhibits the highest stable temperature
for c-CrNphase up to 900 C. The MPP CrNlmalso requires higher tem-
peratures for the -Cr
2
N phase formation as compared to the dcMS and
PMS CrN lms. Therefore, we conclude that the CrN lms deposited
using the MPP technique exhibited superior oxidation resistance as com-
pared to the lms deposited by the traditional dcMS and PMS techniques.
Since the chemical composition and thickness of the CrN lms are
similar, the oxidation behavior of the CrN lms is largely dependent
on the microstructure, texture and residual stress of the lms,
which are strongly affected by the sputtering techniques.
It has been shown that the dcMS, PMS and MPP CrN depositions
generated different ion energy distributions and ion uxes in the
plasma [7]. The dcMS plasma exhibited low ion energies (b15 eV)
and low ion uxes; the PMS plasma exhibited a wide range of ion en-
ergies (>100 eV) and a moderate level of ion uxes; and the MPP
plasma exhibited low ion energies (b30 eV) but an extensive amount
of ion ux, especially for the metal ions. Therefore, the development
of different microstructures and residual stresses of the CrN lms is
related to different plasma properties (ion energy and ion ux) of
the dcMS, PMS and MPP plasmas. An open columnar structure was
developed in the dcMS lm due to insufcient ion bombardment
(Fig. 1A). The high ion energies of the PMS plasma and the high
metal ion uxes of the MPP plasma provided enhanced ion bombard-
ment on the growing lms, which formed a dense and less columnar
grain featured microstructure. Nevertheless, the large kinetic ion en-
ergies in the PMS plasma (e.g. >100 eV) also easily generated higher
residual stresses and defect densities in the PMS lm [36]. In contrast,
the residual stress of the MPP CrN lm is lower than the PMS CrN lm
because the ion energies of the majority of ions in the MPP plasma
were comparable to those found in the dcMS plasma.
The microstructure and residual stress differences of the CrN lms
showed strong effects on the lm oxidation resistance. The intergra-
nular fracture of the dcMS CrN lm is evident (Fig. 1A), which sug-
gests a weak boundary bonding strength between the columnar
grains. It is not surprising that the opened boundaries along the
long columnar grains can be the diffusion paths for the outward diffu-
sion of the Cr and N species and the inward diffusion of O. The crystal-
line Cr
2
O
3
phase and a large amount of -Cr
2
N phase were detected in
the dcMS CrN lm as early as 600 C. The c-CrN structure was only
thermally stable up to 700 C (Fig. 2A). And the hardness of the
dcMS CrN lm after annealing at 800 C maintained 43% of that of
the as-deposited lm. The oxidation activation energy of the dcMS
CrN lm obtained in the current study is about 116 kJ/mol.
The PMS CrN lm showed the breaking down of the columnar
grain growth with the development of ne granular grains but with
a relatively high residual stress (4.5 GPa) (Fig. 1B). The ne grain
size and higher residual stress of the PMS CrN lm led to a high as-
deposited hardness of 28 GPa. However, the large amount of grain
boundaries increases the intrinsic instability of the nano-structured
state by the occurrence of grain growth at elevated temperatures.
They can also act as outward diffusion paths for N atoms from a ther-
modynamic point of view. The higher residual stress of the PMS CrN
lm also results in an intrinsic instability of the microstructure of
the lms at elevated temperatures because of the lower thermal acti-
vation needed to start recovery in such structures [15]. Consequently,
the PMS CrN lm exhibited a similar oxidation behavior to that of the
dcMS CrN lm. The crystalline Cr
2
O
3
phase and a large amount of -
Cr
2
N phase were detected in the PMS CrN lm at 700 C. The c-CrN
structure was thermally stable up to 800 C (Fig. 2B). And the hard-
ness of the PMS CrN lm after annealing at 800 C was 45% of the
as-deposited lm. The oxidation activation energy of the PMS CrN
lm obtained in the current study is about 141 kJ/mol.
Fig. 8. (A) The parabolic oxidation kinetics for the MPP CrN lms at the temperature
range from 700 C to 900 C, and (B) Arrhenius plot of the dcMS, PMS and MPP CrN
lms annealed at 600 C to 900 C in the ambient air.
3289 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290
The dominant transgranular fracture of the MPP CrN lm suggests
a strong boundary bonding strength between the grains (Fig. 1C),
which is attributed to the dense microstructure. The residual stress
of the MPP CrN lm is 2.5 GPa, which is comparable to that of the
dcMS CrN lm but lower than that of the PMS CrN lm. The dense
structure of the MPP CrN lm can effectively reduce the inward and
outward diffusion rates of the ion species. Combined with the dense
structure effect, the low residual stress in the MPP CrN lm probably
slowed down the phase transformation from c-CrN to -Cr
2
N. As a re-
sult, the MPP CrN lm exhibited superior oxidation resistance than
the dcMS and PMS CrN lms. Only a small amount of crystalline
Cr
2
O
3
and -Cr
2
N phases was detected in the MPP CrN lm at
700 C. The c-CrN structure was thermally stable up to 900 C
(Fig. 2C). And the hardness of the MPP CrN lm after annealing at
800 C was 67% of that of the as-deposited lm. The MPP CrN lm
exhibited an activation energy of 195 kJ/mol. It is considered that
the higher oxidation activation energy value in the MPP CrN lm is
because of the dense microstructure which hinders the diffusion of
ion species through the grain boundaries.
5. Conclusions
The oxidation behavior of the CrN lms deposited by dcMS, PMS
and MPP techniques was studied in the temperature range of 600 to
1000 C. The as-deposited CrN lms exhibited a cubic structure and
similar stoichiometry composition, but with different microstructures
and residual stresses. It was found that the MPP CrN lm exhibited
superior oxidation resistance as compared to the dcMS and PMS
CrN lms. Only a small amount of crystalline Cr
2
O
3
and hexagonal
-Cr
2
N phases was detected in the MPP CrN lm after 700 C. After
annealing at 900 C, the MPP CrN lm exhibited an extremely dense
structure with a strong cubic (311) peak. The MPP CrN lm main-
tained 67% of the as-deposited hardness after annealing at 800 C. In
contrast, the dcMS and PMS CrN lms exhibited a porous structure
with a rapid degradation of the cubic phase after 700 C and 800 C,
respectively. The results showed that all lms exhibited parabolic ox-
idation behavior below 900 C. The oxidation activation energies for
the dcMS, PMS and MPP CrN lms are 116 kJ/mol, 141 kJ/mol and
195 kJ/mol, respectively. The improved oxidation resistance of the
MPP CrN lm is attributed to its dense microstructure and low resid-
ual stress.
Acknowledgments
Support of this research program from the North American Die
Casting Association (NADCA) and Department of Energy (DOE-OIT)
is gratefully acknowledged.
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3290 J. Lin et al. / Surface & Coatings Technology 206 (2012) 32833290

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