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Surface & Coatings Technology 202 (2008) 3360 3366

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Influence of substrate bias, deposition temperature and post-deposition

annealing on the structure and properties of multi-principal-component
(AlCrMoSiTi)N coatings
Hui-Wen Chang a , Ping-Kang Huang a , Jien-Wei Yeh a,,
Andrew Davison a , Chun-Huei Tsau b , Chih-Chao Yang c
a

Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300, Taiwan
b
Institute of Materials Science and Manufacturing, Chinese Culture University, Taipei 111, Taiwan
Nano-Powder and Thin Film technology Center, Industrial Technology Research Institute, Tainan 70955, Taiwan
Received 19 September 2007; accepted in revised form 11 December 2007
Available online 23 December 2007

Abstract
Nitride films are deposited from a single equiatomic AlCrMoSiTi target by reactive DC magnetron sputtering. The influence of the substrate
bias and deposition temperature on the coating structure and properties are investigated. The bias is varied from 0 to 200 V while maintaining a
substrate temperature of 573 K. And the temperature is changed from 300 to 773 K whilst maintaining a substrate bias of 100 V. From X-ray
diffraction analysis, it is found that all the as-deposited coatings are of a single phase with NaCl-type FCC structure. This is attributed to the high
mixing entropy of AlN, CrN, MoN, SiN, and TiN, and the limited diffusion kinetics during coating growth. Specific aspects of the coating, namely
the grain size, lattice constant and compressive stress, are seen to be influenced more by substrate bias than deposition temperature. In fact, it is
possible to classify the deposited films as large grained (~ 15 nm) with a reduced lattice constant (~ 4.15 ) and low compressive residual stresses
for lower applied substrate biases, and as small grained (~4 nm) with an increased lattice constant (~ 4.25 ) and high compressive residual
stresses for applied biases of 100 V or more. A good correlation between the residual stress and lattice constant under various deposition
conditions is found. For the coatings deposited at 100 V, and at temperatures above 573 K, the hardness could attain to the range of 32 to 35 GPa.
Even after annealing in vacuum at 1173 K for 5 h, there is no notable change in the as-deposited phase, grain size or lattice constant of the coatings
but an increase in hardness. The thermal stability of microstructure is considered to be a result of the high mixing entropy and sluggish diffusion of
these multi-component coatings. For the anneal hardening it is proposed that the overall bonding between target elements and nitrogen is enhanced by
thermal energy during annealing.
2007 Elsevier B.V. All rights reserved.
Keywords: Nanostructure; High-entropy alloys; Nitride coatings; Sluggish diffusion; Anneal hardening; Thermal stability

1. Introduction
The majority of work pertaining to vacuum deposited nitride
coatings appears to be limited to ternary or, at most, quaternary
systems [17]. However, based on the principle of high-entropy
alloys (HEAs), which contain at least five principal elements in
near equimolar proportions, and the promising properties of
suitably designed HEAs, such as (i) good thermal stability,
Corresponding author. Tel.: +886 3 5742621 33868; fax: +886 3 5722366.
E-mail address: jwyeh@mx.nthu.edu.tw (J.-W. Yeh).
0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2007.12.014

(ii) high hardness and (iii) superior corrosion resistance [813],

it is envisaged that such multi-element materials may be
advantageous in the use as protective coatings. In an initial
study of nitride coatings deposited by reactive magnetron
sputtering from HEA targets, namely FeCoNiCrCuAlMn,
FeCoNiCrCuAl0.5, FeCoNiCrCuAl2 and SiNiCrTiAl targets, it
was found that the coatings possessed relatively low hardnesses
of 15 GPa or less [14,15]. The low hardnesses of these coatings
can be associated to the high content of non-nitride forming
elements and their amorphous structures. It was found that the
hardness of virtually stoichiometric nitride coatings deposited

H.-W. Chang et al. / Surface & Coatings Technology 202 (2008) 33603366

3361

from HEA targets with only nitride forming elements, that is

AlCrTaTiZr [16,17] and AlCrTiSiV [18], had increased hardnesses of about 35 GPa and 30 GPa, respectively. From X-ray
diffraction (XRD) studies, these stoichiometric nitride coatings
were also found to exhibit a single FCC structure [1618].
In the present work, nitride coatings shall be deposited from
a single equiatomic AlCrMoSiTi target by reactive DC magnetron sputtering. The influence of deposition temperature, substrate bias, and post-deposition heat treatments in vacuum on
the structure and properties of the coatings shall be assessed.
2. Experiment
The Si (001) wafer substrates were cleaned sequentially in
acetone, pure alcohol and de-ionized water. The substrates were
placed approximately 12 cm from the target on the centre of a
substrate table that was rotated at a speed of 5 rpm. Prior to
deposition, both the substrate and target were independently
sputter cleaned by means of a shutter placed between them. The
films were deposited from an equiatomic Al20Cr20Mo20Si21Ti19
target by DC magnetron sputtering operated at a power of 150 W.
The base pressure of the system was better than 2.7 10 3 Pa. The
working pressure was 0.67 Pa, with the nitrogen and argon gas
flow rates each fixed at 20 sccm.
When investigating the influence of substrate bias (0
(grounded), 50, 100, 150, and 200 V), the deposition
temperature was held at 573 K. The current densities, respective
to the aforementioned voltages, were recorded to be 0.14, 0.33,
0.36, 0.39, and 0.40 mA/cm2. Likewise, the substrate bias was
fixed at 100 V (0.36 mA/cm2) when investigating the affects
of deposition temperature (300, 473, 573, 673, and 773 K).
Annealing was carried out for 5 h in an evacuated quartz tube
(1.3 Pa).
The film thicknesses, measured by an -step device, were
within the ranges of 1.1 to 1.4 m and 1.4 to 1.7 m when
examining the effects of substrate bias and deposition temperature, respectively. The structure of the films was characterized using X-ray diffraction (MAC Science MXP18 XRD
spectrometer) with a glancing angle of 1, using a copper target
(k1 wavelength = 0.15406 nm). The composition of the films
was determined by an energy dispersive X-ray analyzer
(EDXA) (JEOL JSM-5410) and electron microprobe analyzer
(EPMA) (JEOL JAX-8800). The hardness and modulus of the
coatings were measured by nano-indention (XP System MTS).
The stress was determined using the substratecurvature
technique and applying Stoney's equation.
3. Results and discussion
3.1. As-deposited coatings
3.1.1. Topography
In Fig. 1(a) it is seen that the roughness decreases with
substrate bias until it reaches a minimum of about 0.3 nm
at 100 V. The decrease in surface roughness with bias is
ascribed to an increase in the atomic movement and densification of the coating material as a result of the increased flux and

Fig. 1. Surface roughness as a function of (a) substrate bias and (b) deposition
temperature.

energy of the ions flux [19]. As shown in Fig. 1(b), the

roughness is seen to be around 0.3 nm and 1.25 nm at the lower
and higher deposition temperatures, respectively. The increase
in surface roughness at the higher deposition temperatures is
suggested to result from the grain growth effect. Nevertheless,
as the original substrate surface roughness is around 1 nm and
the film thicknesses are about 1.5 m, all these measured
roughnesses are low.
3.1.2. XRD
3.1.2.1. Crystal structure. From XRD analysis, shown in
Figs. 2(a) and (b), it is found that all of the coatings, which have
close to the same amount of each target element and stoichiometric
nitride compositions, i.e. ~Al0.2Cr0.2Mo0.2Si0.2Ti0.2 N, exhibit
only a single FCC structure of NaCl-type. This indicates that FCC
structure has a large accommodation of other non-FCC binary
nitrides since only TiN (a = 4.24 ) and CrN (a = 4.14 ) are FCC
nitrides and AlN (HCP), MoN (HCP) and Si3N4 (hexagonal
structures, which are built up by corner-sharing SiN4 tetrahedra)
are non-FCC ones.
It has been determined that as-deposited mixtures of FCC
forming ternary nitrides, i.e. ZrxTi1 xN [2], CrxTi1 xN [2,4],
MoxTi1 xN [4], NbxTi1 xN [4], and WxTi1 xN [4], have a single
FCC solid-solution structure across the entire composition range.
Additionally, a single FCC solid-solution has been reported to
form for approximately 60 to 70% of Al in both TixAl1 xN and

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H.-W. Chang et al. / Surface & Coatings Technology 202 (2008) 33603366

deposited ternary coatings, phase separation after annealing in

the TixAl1 xN [26] and ZrxTi1 xN [27] systems, at about
1200 K, reflects that many of them are likely to be of a metastable nature. The tendency to deposit coatings with a single
metastable FCC nitride phase has been considered to be a result
of limited diffusion kinetics, in which the elements cannot reach
their stable configurations [20]. However, the single as-deposited FCC phase of the present nitride is not simply due to
kinetic reason. It is believed to also relate with the high mixing
entropy effect since the mixing of five kinds of different binary
nitrides to form the FCC nitride solution might give large
mixing entropy to counterbalance the positive mixing enthalpy
due to lattice distortion and different crystal tendency, and thus
inhibit the phase separation. This preference of FCC solution
phase could be supported by its thermal stability with which it
didn't show any decomposition under XRD resolution level
even after annealed at 1173 K for 5 h, as will be seen in Section
3.2. Although mixing entropy effect is expected to be smaller
at lower temperatures and favor phase separation, sluggish
diffusion effect due to five different species and lower thermal
energy is involved to retard phase separation. This phenomenon
demonstrates that the high entropy and sluggish effects in
stabilizing the solid-solution phase for high-entropy alloys also
occur in multi-component nitrides [813].

Fig. 2. XRD patterns of the coatings deposited at different (a) substrate biases
and (b) substrate temperatures.

CrxAl1 xN coatings, in which Al atoms are considered to occupy

Ti lattice sites [2,3]. Single as-deposited FCC structures have in
fact been predicted in various theoretical works for a high
proportion of AlN mixed with an FCC forming nitride
component, i.e. TiAlN, CrAlN, ZrAlN, etc. [2024]. Nevertheless, there appears to be some inconsistencies for both the
theoretically predicted and experimentally determined solubility
limits of HCP AlN in an FCC structure. For example, it was
predicted by Makinoa [23] that the solubility limits of AlN within
the FCC structures of HfN, ZrN, NbN, and WN are only 21, 33,
53, and 54%, respectively. These values given for HfN and ZrN
are far lower than those predicted by Holleck [20], which was in
the range of about 60 to 70% for both. From deposition studies of
ZrAlN by Makinao, it was determined that the solubility limit of
AlN in FCC ZrN was 30 to 35%, which is in agreement to his
predicted value. However Holleck [20] and Sanjines [24] reported
that even up to 42 and 50%, respectively, of AlN in ZrN a single
FCC was observed these aluminum contents being the
maximum studied. The contradiction between these works may
originate from the deposition conditions employed; for example,
Makinao [25], who reported a particularly low-solubility limit of
AlN in FCC ZrAlN, deposited the films under unconventionally
highly-enhanced deposition conditions.
Although there appears to be a general lack of information
pertaining to the thermal stability of single-phased FCC as-

3.1.2.2. Lattice parameter. The majority of the present coatings are determined to have a lattice constant of about 4.25 .
Those deposited at biases of less than 100 V, however, have a
smaller lattice constant of 4.15 (Fig. 2(a)). As these coatings
have comparable compositions, the change in lattice constant
must be a result of other factors. It has been found that both
TiSiAlN and TiAlN FCC solution phases, with lattice constants
of 4.19 and 4.29 , respectively, can exist within the same asdeposited TiAlSiN films [6]. The formation of the TiAlN solution phase in these coatings was attributed to deposition conditions that increased adatom mobility during film growth, i.e. a
higher substrate temperature and/or reduced deposition rate,
therefore permitting the segregation of Si to form a separate
amorphous Si3N4 phase. Furthermore, the segregation of an
amorphous Si3N4 phase was considered to inhibit grain growth
in the as-deposited films [6]. With reference to the present
coating system, it appears that the increase in the lattice constant
as well as the reduction in grain size concur with deposition
conditions under which adatom mobility is possibly increased,
i.e. at higher applied substrate biases for a given deposition
temperature. Nevertheless, for the present coatings, even though
a wide range of substrate conditions have been examined, only
a single FCC nitride phase can be identified in any one individual coating. Adatom mobility will also be expected to be
reduced at the lower deposition temperatures of 300 and 473 K,
yet these coatings still possess the larger lattice constant and the
smallest grain sizes (Fig. 2(b)). Both of these factors suggest
that the changes in lattice constant of the present coatings do not
concur with the segregation of Si, as reported in the TiAlSiN
system [6].
An alternative explanation for the increased lattice constant
at higher substrate biases is the enhanced flux and energy of the

H.-W. Chang et al. / Surface & Coatings Technology 202 (2008) 33603366

3363

bombarding ions, whereby Frenkel pairs and anti-Schottky defects are induced by the ion peening effect [2830]. From
Fig. 3, the good correlation between two coating properties
which are mutually increased by the presence of Frenkel pairs
and anti-Schottky defects, i.e. the lattice constant (determined
from the Scherrer equation using XRD data) and the compressive residual stress (measured by the curvature technique),
implies that the change in lattice constant is a result of the ion
peening effect as opposed to segregation of a Si3N4 phase. That
is to say, even though the present system contains several
immiscible nitrides, for example AlN, TiN and Si3N4, it appears
to retain a single solid-solution structure, even at a deposition
temperature of 773 K (maximum permissible in the present
system) and an applied substrate bias of 200 V. This in fact
agrees with the XRD observation that the as-deposited nitrides
are single FCC phases.
3.1.2.3. Grain size. The decreased grain size at the higher
substrate biases, as shown in Fig. 2(a), can be related to an increase
in the nucleation rate at ion-induced surface defects [31,32], as
opposed to phase segregation. For the coatings deposited at different temperatures, which are all biased at 100 V, it is seen in
Fig. 2(b) that as long as a sufficiently high substrate temperature is
used, i.e. 573 K, the coatings have a grain size of about 4 nm. This
would appear to suggest that the grain size is most influenced by
the ion-induced nucleation rate as opposed to the changes in grain
growth kinetics expected at different temperatures. The smaller
grain size at the lowest deposition temperatures is considered to be
a result of both a reduction in the critical nuclei size and the
reduced energy for grain growth [33].
3.1.3. Mechanical properties
In Fig. 4(a), it is seen that the residual stress of the coatings
biased at 0 and 50 V is only slightly compressive, with values of
about 0.3 GPa. The coatings deposited at substrate biases
of 100 V or higher, however, have compressive stresses of
around 3 GPa. The coatings deposited at different temperatures
also possess compressive stresses of about 3 GPa, as shown in

Fig. 3. Lattice constant as a function of compressive residual stress. The point

enclosed by the circle is not from the present work, and was deposited at a higher
nitrogen flow rate ratio of 67% (same total pressure) with a substrate bias and
temperature of 50 V and 573 K, respectively.

Fig. 4. Residual stress determined as a function of (a) substrate bias and (b) deposition
temperature.

Fig. 4(b), which is considered to be a result of the fact that they too
are biased at 100 V. The increase in compressive residual stress
at higher applied substrate biases is attributed to an increase in the
ion peening effect that leads to atoms being knocked deeper into
the film, where they become trapped creating Frenkel pairs and
anti-Schottky defects [2830]. By applying the rule of mixtures to
determine the coefficient of thermal expansion (CTE) of the
coating as a whole from each of the constituent binary nitride
components, it is determined that the mismatch between the CTE
of the coating and silicon substrate would lead to greater tensile
residual stresses at higher deposition temperatures. It is thus
surprising that the opposite appears to occur in Fig. 4(b), whereby
the residual stress is seen to become more compressive at higher
substrate temperatures. As all discharge conditions are held constant, the energetic species arriving at the growing film from the
discharge will be the same, regardless of the deposition temperature. The higher compressive stresses, therefore, is thought to be
a result of thermally-enhanced crystallinity and bonding strength
between target elements and nitrogen, which aid the grain growth.
As the grain boundary fraction decreases, grain boundary sliding
effects are reduced and thus higher compressive stresses can be
generated during film growth. Both the crystallinity and stronger
MN bonding is also reflected by the hardness and the elastic
modulus since both increase with increasing substrate temperature (see next paragraph).
The hardness and modulus are shown as functions of substrate bias and deposition temperature in Figs. 5(a) and (b),

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H.-W. Chang et al. / Surface & Coatings Technology 202 (2008) 33603366

3.2. Vacuum annealing

Based on XRD analysis, it is possible to group the as-deposited
coatings as being (i) [V 50] large grained (~15 nm) with a small
lattice constant (4.15 ), and low compressive stresses
(b0.5 GPa), or (ii) [V 100] as having small grains (b4 nm), a
large lattice constant (~4.26 ), and high compressive stresses
(N2.5 GPa). Coatings belonging to each of these groups shall
therefore be annealed in vacuum for 5 h at different temperatures
to assess and compare their thermal stability.
The XRD diffraction patterns of the V 50 and V 100 films
annealed at different temperatures in an evacuated quartz tube
are shown in Fig. 6(a) and (b), respectively. It can be seen that
both the coatings not only don't decompose into other new
phases but also retain their original structure in terms of the
preferred orientation, lattice constant, and grain size even after
annealing at 1173 K for 5 h.
The stable FCC solution phase without any XRD detectable
phase separation up to 1173 K has been attributed to the high
mixing entropy effect as discussed in Section 3.1.2.1. From
thermodynamics, it is well known that entropy effect becomes
more important at elevated temperatures and thus decreases the
free energy of the FCC solution phase.
The nearly unchanged lattice constants of the V 50 and V 100
as-deposited films after annealing imply that stress relaxation

Fig. 5. Hardness, modulus and (inset) the hardness/modulus ratio as a function

of (a) substrate bias and (b) deposition temperature.

respectively. In Fig. 5(a) the modulus is observed to initially decrease, but then maintain a constant value for a bias of
100 V or greater. The hardness on the other hand initially
increases to a maximum of about 33 GPa at 100 V, beyond
which it decreases. The maximum in hardness attained at
100 V is attributed to the slightly greater grain size than those
deposited with a higher applied bias and greater compressive stress of those deposited at the lower biases. The similar
hardness of the coatings deposited at the lowest and highest
substrate biases is credited to the coatings with the increased
compressive stress, i.e. deposited at higher applied biases, having their hardness limited by their smaller grain size, i.e. the
inverse HallPetch effect [34], i.e. a balance between grain size
and residual stress on the measured hardness. The reduction in
the hardness of the coatings deposited at the lower substrate
temperatures, as shown in Fig. 5(b), is also attributed to their
smaller grain size, and thus the inverse HallPetch effect [34].
The hardnesses of around 34 GPa for the coatings deposited
at higher temperatures are ascribed to their greater grain size,
denser structures, and increased compressive stress. As a result
of its relatively high hardness and low modulus, the greatest
ratio between these two mechanical properties, shown in Fig. 5
(a) and (b), is obtained for the coating deposited at 100 V and
573 K. The hardness to modulus ratio has been found to be a
good indicator of the performance of a coating under a number
of wear conditions [35].

Fig. 6. X-ray spectrum of the (a) V 50 and (b) V 100 films annealed for 5 h at
different temperatures in a sealed quartz tube at 1.33 Pa.

H.-W. Chang et al. / Surface & Coatings Technology 202 (2008) 33603366

due to defect annihilation is very small. It has been reported that

the compressive stress of the as-deposited coatings is reduced
after annealing, as noted from a shift in the XRD peak position
[36]. This is attributable to the diffusion of implanted atoms to
the surface, hence the annihilation of the stress inducing defects
[36]. Nevertheless, this is not observed in the present coating
system, for which there is an insignificant change in the XRD
peak position, even after annealing for 5 h up to 1173 K. This is
reasonable since diffusion in these multi-component coatings is
sluggish to prevent the migration of defects to the surface, and
hence prevents stress relaxation. Similarly, sluggish diffusion
might be also used to explain why the preferred orientation and
grain size are almost unchanged.
Unlike the decrease in hardness found for coatings undergoing
stress relaxation [36,37], there is an increase in the hardness after
annealing of the present coatings, as shown in Fig. 7. Such an
increase in the hardness after annealing has been reported to be a
consequence of phase segregation in as-deposited metastable
single-phased FCC nitride coatings, such as TiAlN [26], ZrTiN
[27], and TiSiN [38]. Based on its greater incompatibility with the
other nitride components present, as inferred from theoretical
studies of segregation in TiAlN [21,22] and TiSiN [39] coatings,
the segregation of SiN is most likely in the present coatings. But as
it cannot be resolved in XRD analysis, its volume fraction would
be too low to account for the hardening effect. One more evidence
ruling out the significant segregation of SiN is that obvious
hardening during annealing can be obtained even at 773 K which
is too low to form the segregation. Thus, it is proposed that anneal
hardening phenomenon comes from the enhancement of overall
bonding between target elements and nitrogen by thermal energy
during annealing.
4. Conclusions

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

(viii)

From the deposition of ~ Al0.2Cr0.2Mo0.2Si0.2Ti0.2N0.5 films

at a range of substrate temperatures and applied substrate biases,
and through vacuum annealing treatments, it was found that:
(ix)
(i) All of the coatings possess a single FCC structure of
NaCl-type. This indicates that the FCC lattice formed by

3365

FCC forming nitrides can dissolve a large proportion of

non-FCC forming nitrides, i.e. Si, Al, within itself.
As a result of ion-induced defects, the grain size was
reduced at higher substrate biases. Furthermore, as long as
a critical deposition temperature was exceeded, the grain
size was apparently dictated by ion-induced nucleation as
opposed to temperature dependent grain growth kinetics.
The lattice constant and residual compressive stress of the
various coatings, which both increase as a result of enhanced ion peening, had a close correlation. This suggests
that the coatings are of a predominantly single as-deposited solution phase.
In contrary to that expected from considerations to the
CTE of the coatings, the compressive residual stresses
actually increase for higher deposition temperatures. This
is attributable to the thermally-enhanced crystallinity and
increased bonding strength between target elements and
nitrogen, which aid the grain growth and thus reduce
grain boundary sliding effects in relaxing compressive
stresses.
Even though the coatings deposited at the lowest applied
substrate biases have a smaller inherent compressive stress
compared to those deposited at the highest biases, they
possess similar hardnesses. This is considered to be a
result of the larger grain size of the lower biased coatings
compensating for their reduced compressive stresses.
The coatings deposited at an applied bias of 100 V, and
deposition temperature higher than 573 K, have the highest hardnesses of about 34 GPa.
The coatings deposited at the lowest temperatures have
the lowest hardnesses on account of the inverse Hall
Petch effect due to their very small grain size.
The lattice constant is not found to significantly change after
annealing at 1173 K for 5 h in vacuum. This is considered to
be a result of the prevention of stress relaxation by the
diffusion of defects to the surface due to the sluggish diffusion in these multi-component nitride coatings.
The hardness of the coatings, however, is found to increase
after annealing, which suggests that the overall bonding
between target elements and nitrogen is enhanced by thermal energy during annealing.

Acknowledgements
The authors gratefully acknowledge the financial support for
this research from the National Science Council of Taiwan under
grants NSC-93-2120-M-007-006 and the ministry of Economic
Affairs of Taiwan under grant 93-EC-17-A-08-S1-0003.
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Fig. 7. Hardness as a function of annealing temperature for the coatings with

different substrate bias.

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