The microstructure and mechanical properties of TiN\Ni nanocomposite

thin lms
A.M. Pagon , E.D. Doyle, D.G. McCulloch
Applied Physics, School of Applied Sciences, RMIT University, GPO Box 2476V, Melbourne, 3001 Victoria, Australia
a b s t r a c t a r t i c l e i n f o
Article history:
Received 28 December 2012
Accepted in revised form 24 July 2013
Available online 8 August 2013
Keywords:
Nanocomposite thin lms
Filtered cathodic vacuum arc
Transmission electron microscopy
Nanoindentation
The effect of varying substrate bias and temperature on the microstructure and properties of TiN\Ni nanocom-
posite thin lms, fabricated using a ltered cathodic vacuum arc, was investigated. Films deposited at room
temperature with no applied bias had low surface roughness and exhibited ne microstructure. An increase in
bias or temperature resulted in signicant changes in microstructure, including an increase in the crystallinity
of the Ni phase and an increase in TiN and Ni crystallite sizes. At a substrate bias of 500 V, separation of the
TiN and Ni phases was observed resulting from the high-energy ion bombardment. The intrinsic stress and
hardness of the lms were found to decrease with increasing Ni crystallite size. The TiN\Ni nanocomposite
lms were found to exhibit lower hardness than a TiN lm deposited using similar conditions and were more
ductile due to the presence of metallic Ni. The lm deposited at room temperature and low bias was found to
be highly elastic, exhibit reasonable hardness (~18 GPa) and low intrinsic stress. This combination of properties
has the potential for exploitation in a range of tribological applications.
Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
1. Introduction
Over the past 40 years, hard ceramic thin lm coatings such as
titanium nitride (TiN) have signicantly improved the performance of
industrial cutting tools [1]. The materials science underpinning these
productivity gains has to-date focussed largely on improving the
hardness of physically vapour deposited (PVD) coatings. An inevitable
consequence of this trend to ever-harder, even super-hard coatings is
that coatings have become increasingly brittle often containing high
intrinsic stress [2,3]. Such factors can adversely affect tool life
performance, particularly under high impact load conditions, such
those encountered during milling. Recognition of such problems is
evident in the development of multilayer coatings, in which an attempt
is made to arrest crack propagation by introducing inter-phase
boundaries [46]. Also of interest are hard nanocomposite coatings
which resist cracking, have high elastic recovery and lowintrinsic stress
[7,8]. Recent work has shown that hard nanocomposite coatings with
enhanced resistance to cracking are characterised by a ratio of hardness
(H) to effective elastic modulus (E*) of greater than 0.1 and an elastic
recovery of greater than 60% [7].
One method of producing such nanocomposite lms is to reactively
vapour deposit both nitride and non-nitride forming elements [914].
One such non-nitride forming element is Ni, which has been used in
the fabrication of nanocomposites [1517]. For example, TiN\Ni nano-
composite thin lms have been produced by several methods including
magnetron sputtering [18], dual ion beam assisted deposition [19] and
cathodic arc [20,21]. The thin lms exhibited a range of microstructures
depending on the deposition conditions and promising mechanical
properties, which have the potential for improved tribological perfor-
mance in metal cutting applications. However, the above studies did
not undertake detailed microstructural analysis using cross sectional
transmission electron microscopy (TEM), which limits the fundamental
understanding of structure, hence properties and application. This is
critically important, since in the production of nanostructured lms,
by physical vapour deposition (PVD), holds the possibility of producing
unique, non-equilibrium compositions and novel structures [22].
In this study, TiN\Ni nanocomposite thin lms were fabricated
using a ltered cathodic vacuum arc (FCVA) system tted with a single
cathode composed of 50:50 at.% Ti:Ni. The motivation was to produce
coatings suitable for exploitation as layers in functionally graded coat-
ings [23] where the property mismatch between substrate and hard
coating is reduced by using one or more interlayers with intermediate
or graded properties such as, ductility, residual stress and hardness.
FCVA is a vapour deposition method in which the average energy of
the highly ionised depositing ux is controllable by varying the
substrate bias voltage. This deposition energy is known to inuence
the type of microstructure produced [24], which in turn, determines
the resulting physical properties. Previous work on TiN\Ni nanocom-
posite thin lms using cathodic arc [20,21] employed a dual cathode
system (one Ti and the other Ni doped with 10 at. % Cr) to produce
thin lmcoatings and concentrated mainly on the effect of post deposi-
tion annealing on grain size. Here, the results of varying the substrate
bias and deposition temperature on the microstructure and mechanical
properties of TiN\Ni thin lms, are presented. This is supported with
detailed microstructural characterisation using a range of techniques
Surface & Coatings Technology 235 (2013) 394400
Corresponding author at: Applied Physics, School of Applied Sciences, RMITCity
Campus, GPO Box 2476V, Melbourne, 3001 Victoria, Australia. Tel.: +61 3 9925 2356;
fax: +61 3 9925 5290.
E-mail address: arwen.pagon@rmit.edu.au (A.M. Pagon).
0257-8972/$ see front matter. Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.surfcoat.2013.07.051
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including direct observation of the cross sectional microstructure of the
thin lms using transmission electron microscopy (TEM). Also, struc-
tureproperty relationships were determined using nanoindentation.
2. Experimental
Films were prepared using an FCVA deposition system, which is
described elsewhere [25], using a rotating cathode operating at an arc
current of 100 A. The plasma emanating from the cathode was directed
through a magnetic double bend lter, designed to minimise the
deposition of macroparticles and neutral species. Films were deposited
onto polished silicon wafer substrates that were cleaned with acetone
andethanol prior to deposition. Stationary substrates were either biased
by mounting on a steel holder connected to a variable DC voltage supply
(b1 kV) or heated by mounting on a heater stage with the temperature
monitored using a thermocouple. The temperature to which the
substrates are initially heated before deposition is referred to as the
deposition temperature. The system was pumped to a base pressure of
less than 10
3
Pa before each deposition. A Ti
50
:Ni
50
at.% cathode was
used and a series of thin lms was produced using the conditions
shown in Table 1. All lms were prepared at an operating pressure of
0.2 Pa. TiN\Ni lms were prepared in an N
2
processing gas. A TiNi
lm was also prepared at oating potential and room temperature in
Ar processing gas. For comparison purposes, a TiN thin lm was
produced from a Ti cathode in N
2
atmosphere at the same arc current
and operating pressure.
The intrinsic stress of the thin lms was obtained using Stoney's
equation [26] after measuring the radii of curvature of the substrates
before and after deposition using a Tencor surface proler. The thick-
ness of the thin lms was also determined using surface prolometry.
Scanning electron microscopy (SEM) and atomic force microscopy
(AFM) were used to study the surface morphology of the thin lm
coatings. A FEI Nova Nano SEM with eld emission gun source was
used in high vacuum mode with a working distance of 5 mm and
accelerating voltage of 15 kV were used to obtain the SEMmicrographs
of the thin lmsurfaces. Surface roughness was measured using a Veeco
Dimension 3100 AFM operated in tapping mode. AFM scans were
performed over several different sized areas ranging from 3 3 m
square to 10 10 m square to obtain an average RMS roughness
value for each sample.
The composition of the thin lms, as a function of depth, was
determined by x-ray photoelectron spectroscopy (XPS) depth proling
using a Thermo Scientic K-Alpha Spectrometer with an Al anode x-ray
source. The XPS sputter depth proles were performed using an Ar ion
beam operating at 12 keV etching approximately a 1 mm
2
area and
the x-ray spot size used for analysis was 200 m.
Table 1
Summary of the deposition parameters and several characteristics of the lms deposited.
Film type Bias
(V)
Temperature
(C)
Thickness
(nm)
Deposition rate
(nm/min)
Roughness
(nm)
TiNi Floating Room temp. 300 34 0.9
TiN\Ni Floating Room temp. 200 100 0.9
TiN\Ni 200 Room temp. 330 85 4.4
TiN\Ni 500 Room temp. 70 14 4.3
TiN\Ni Floating 250 240 80 3.3
TiN\Ni Floating 500 150 50 8.9
TiN Floating Room temp. 270 50 0.9
(a) (b)
(c) (d)
Fig. 1. XPS depth proles of the lms deposited at (a) oating potential-roomtemperature in Ar and the lms prepared inN
2
at (b) oating potential-roomtemperature, (c) 500 V bias-
room temperature and (d) oating potential-500 C.
395 A.M. Pagon et al. / Surface & Coatings Technology 235 (2013) 394400
X-ray diffraction data was collected using a Bruker D8 DISCOVER
microdiffractometer tted with a GADDS (General Area Detector
Diffraction System), using CuKalpha radiation (1.54 wavelength;
40 kV potential; 40 mA current), and ltered with a graphite mono-
chromator in the parallel mode (175 mm collimator with 0.5 mm
pinhole).
Cross-sectional samples were prepared using a combination of
mechanical polishing and Ar ion beam etching to obtain a thin area for
observationinthe TEM. The microstructure of the thinlms was studied
using a JEOL2010 TEM tted with a LaB
6
lament and operating at
200 kV. Energy ltered TEM (EFTEM) was also performed using a
Gatan imaging lter to obtain cross sectional element maps.
The mechanical properties of the thin lms were studied using a
Hysitron 950 Triboindenter tted with a diamond Berkovich indenta-
tion tip. To determine H and E*, twenty-ve indents were made up to
a maximum force of 1400 N and hardness values were calculated
using the Oliver and Pharr method [27]. The ductility of the coatings
was evaluated by calculating the elastic recovery (W
e
) from the load
unload curves [8].
3. Results and discussion
3.1. Deposition rate
The deposition rate for the TiNi thin lm deposited in an Ar
atmosphere was approximately 34 nm/min (see Table 1). This
increased to 100 nm/min when an N
2
atmosphere was used and
incorporated into the growing thin lm. The application of a substrate
bias resulted in a decrease in deposition rate as a result of sputtering
at the substrate due to ion bombardment. The effects of sputtering are
most evident at a substrate bias of 500 V where the deposition rate
dropped to 14 nm/min. A decrease in deposition rate was also observed
with an increase in substrate temperature. Aconsequence of the latter is
that there is an increase in the energy of the surface atoms which,
combined with the high potential energy of the arriving ions can
cause surface atoms to be emitted [24].
3.2. Composition
Fig. 1 shows XPS depth proles from selected lms and Table 2
shows the average elemental composition of all the lms with the
exception of the lm deposited at 500 V because the composition
varied as a function of depth (Fig. 1(c)). The depth prole of the thin
lm deposited in Ar atmosphere (Fig. 1(a)) shows that the concentra-
tion of Ti and Ni remains relatively constant throughout its thickness
with average values of 32 at.% and 52 at.% respectively. The Ti:Ni ratio
in the lm is approximately 38:62 which indicates that the thin lm is
Ni rich as expected due to the higher ablation rate of Ni from the
cathode compared to Ti [28]. This thin lm also contained a relatively
high concentration of oxygen (~16 at.%) due to the highly reactive
nature of Ti. The lm deposited under the same conditions in a N
2
environment (Fig. 1(b)) had a similar Ti:Ni ratio with approximately
32 at.% N. A low level of oxygen (~4 at.%) is also present in this lm,
indicating that the presence of N
2
reduces the reactivity of the Ti with
oxygen.
When a bias of 200 V is applied to the substrate, the ratio of Ti to
Ni is approximately 45:55. The decrease in the Ni content when
compared to the lms deposited at oating potential is consistent
with preferential sputtering of the Ni. Fig. 1(c) shows the effect on the
composition of increasing the substrate bias to 500 V where there is
evidence of a large increase in Ni close to the substrate. This indicates
elemental segregation has occurred under conditions of high substrate
bias. The lms deposited with 200 V and 500 V substrate bias
showed no evidence of oxygen throughout the thin lm. The absence
of oxygen within the lms can be attributed to preferential sputtering
of oxygen.
The thin lms deposited at elevated temperature had a Ti:Ni ratio of
44:56 similar to that of those deposited withapplied bias. Inthis case the
decrease in Ni content can be attributed to the increased vapourisation
Ni atoms preferentially to Ti due to differences in their cohesive energy
[28]. The thin lms deposited at 250 C and 500 C contained approxi-
mately 13 at.% and 18 at.% oxygen respectively. This is much higher
than that observed for the thin lms deposited at room temperature
due to higher levels of porosity (see Section 3.4).
3.3. X-ray diffraction
Fig. 2 shows XRD diffractograms of all the lms. It should be noted
that all of the diffractograms show a high intensity peak at approxi-
mately 70 which originates from the silicon substrate. Note that each
diffractogram was normalised to the most intense peak originating
from the lm.
The diffractogramfromthe TiNi lm(Fig. 2(a)) was found to exhibit
broad, low intensity peaks indicating that the lm is highly disordered.
The most prominent feature is at approximately 42 (indicated by an
arrow) and could not be indexed to any specic phase. A similar result
Table 2
Elemental concentrations and Ti:Ni ratios of the thin lms.
At. %
Film type Bias (V) Heater temperature (C) Ti Ni N O Ti:Ni ratio
TiNi Floating Room temp. 32 52 16 38:62
TiN\Ni Floating Room temp. 27 38 32 4 40:60
TiN\Ni 200 Room temp. 30 38 32 0 45:55
TiN\Ni Floating 250 25 32 30 13 44:56
TiN\Ni Floating 500 26 33 24 18 44:56
TiN Floating Room temp. 44 0 46 10 100:0
Fig. 2. XRD diffractograms of the lms deposited at (a) oating potential-room tempera-
ture in Ar and the lms prepared in N
2
at (b) oating potential-room temperature,
(c) 200 V bias-room temperature, (d) 500 V bias-room temperature, (e) oating
potential-250 C and (f) oating potential-500 C. The intense peak at 2 ~ 70 is due to
the silicon substrate.
396 A.M. Pagon et al. / Surface & Coatings Technology 235 (2013) 394400
was previously found for TiNi thin lms deposited at low bias using an
unltered cathodic arc [29]. The most intense peak in the diffractogram
for the lm deposited in N
2
at oating potential-room temperature
(Fig. 2(b)) is the {200} TiN peak, indicating that the TiN phase has a
preferred orientation. The asymmetry of the TiN {200} peak suggests
the presence of some crystalline Ni {111}. The surface energy
minimisationmodel by Hultmanet al. [30] and later Knuyt [31] suggests
that atoms will arrange into crystalline planes with the lowest possible
surface energy as the lm grows. In the case of TiN, the {200} planes
have the lowest surface energy per unit area and therefore this model
predicts that the {200} preferred orientation will be favoured as
observed in Fig. 2(b).
At a substrate bias of 200 V (Fig. 2(c)) peaks for both the TiN and
Ni phases are more clearly evident. This indicates that substrate bias
promotes crystallisation of both phases. At 500 V (Fig. 2(c)) the
main peaks observed are the {111} reections for both TiN and Ni. The
change in preferred orientation of the TiN from {200} to {111} at high
bias can be explained by the differences in sputter yield for these differ-
ent orientations. Since sputter yield is inversely proportional to surface
energy [32], the lm is expected to grow with the TiN {111} planes
parallel to the substrate surface under high bias conditions.
At a substrate temperature of 250 C, the XRD diffractorgram
(Fig. 2(e)) is similar to that of the thin lm deposited at room
temperature in N
2
(Fig. 2(b)). However, for this thin lm the Ni peaks
are more prominent, indicating that the Ni is more crystalline. At
500 C (Fig. 2(f)) Ni peaks are much sharper, particularly for the {111}
reection, indicating that the higher temperature has caused a further
increase in crystallisation.
3.4. Microstructure
Cross-sectional TEMimages of all the lms are showninFig. 3 (bright
eld) andFig. 4 (dark eld). The lmdepositedinAr (Fig. 3(a)) shows an
amorphous microstructure, in agreement with the XRD. The highly
disordered nature of this lm is conrmed in the selected area diffrac-
tion pattern and dark eld image shown in Fig. 4(a). The lm deposited
at oating potential-room temperature in N
2
(Fig. 3(b)) exhibits a very
ne-grained microstructure, which is uniform throughout the thickness
of the lm. The diffraction pattern for this lm (Fig. 4(b)) shows
preferred orientation in which the {200} TiN planes are aligned perpen-
dicular to the direction of lm growth. The dark eld image taken from
this reection highlights these crystallites and shows a ne structure
with crystals b10 nm in size. No evidence of crystalline Ni is observed
in the diffraction pattern, suggesting that the bulk of the Ni is present
in a highly disordered form.
Fig. 3. Cross-sectional TEM images (taken in bright eld) of the lms deposited (a) in Ar
and the lms prepared in N
2
at (b) oating potential-room temperature, (c) 200 V
bias-room temperature, (d) 500 V bias-room temperature, (e) oating potential-
250 C and (f) oating potential-500 C.
Fig. 4. Cross-sectional TEM images (taken in dark eld) with inset diffraction patterns
(arrow indicated the position of the dark eld aperture) of the lms deposited (a) in Ar
and the lms prepared in N
2
at (b) oating potential-room temperature, (c) 200 V
bias-room temperature, (d) 500 V bias-room temperature, (e) oating potential-
250 C and (f) oating potential-500 C. The diffraction patterns are indexed to TiN and
Ni where 1 = {111} TiN, 2 = {200} TiN, 3 = {220} TiN, a = {111} Ni and b = {200} Ni.
397 A.M. Pagon et al. / Surface & Coatings Technology 235 (2013) 394400
The effect of applying a substrate bias of 200 V on the microstruc-
ture is shown in Figs. 3(c) and 4(c). The bright eld image (Fig. 3(c))
shows a coarser microstructure than the thin lm prepared at oating
potential (Fig. 3(b)). This lmalso exhibits a {200} preferred orientation
for the TiN(Fig. 4 (c)). Reections fromcrystalline Ni are observed in the
diffraction pattern in agreement with the XRD. The dark eld image
shows that this thin lm grows with a ne grain structure, similar to
the thin lm deposited at oating potential, for approximately the rst
50 nm, which then gives way to a coarser microstructure for the
remainder of the lm growth. This change in growth may be due to ion
bombardment from the higher substrate bias in combination with
some heating of the substrate as the thin lm grows. When the applied
substrate bias is increased to 500 V a further coarsening of grain
structure is observed (Figs. 3(d) and 4(d)). The diffraction pattern
shows the change in preferred orientation from TiN {200} to TiN {111}
consistent with the XRD.
Increasing the substrate temperature to 250 C for a lmdeposited at
oating potential in N
2
(Figs. 3(d) and 4(d)) results in a microstructure
similar to that observed for the lm deposited at 200 V (Figs. 3(c)
and4(c)). At 500 C(Figs. 3(e) and4(e)), the highsubstrate temperature
promotes the growth of large crystals. There is therefore a trend of in-
creasing crystallite size with increasing substrate temperature. The
TEM images of this thin lm clearly show an open porous surface
structure consistent with the high oxygen content in this thin lm
observed in the XPS depth prole (Fig. 1(d)).
Fig. 5 shows pseudo colour EFTEMelemental maps of all the lms. It
is evident in Fig. 5(a) and (b) that in both of the lms deposited at
oating potential-room temperature, all the elements are evenly
distributed throughout the depth of the lms. As the substrate bias is
increased to 200 V (Fig. 5(c)) the initial growth of the lm appears
to be Ni decient, however the bulk of the lm shows resolvable Ni
crystals embedded in TiN. This result is in agreement with the XRD
that shows crystalline phases of TiN and Ni.
At the high bias of 500 V (Fig. 5(d)), large crystals Ni are predom-
inant in the bottom half of the lm adjacent to the substrate. In the
upper half of the lm, TiN is the dominant phase. The authors are un-
aware of any prior publication reporting phase separation, as observed
here. It is reasonable to assume that this phase separation is a
consequence of the high degree of ion bombardment, that occurs during
lm growth at high bias due to increased heating and/or surface and
bulk diffusion effects.
The EFTEMmaps for the lms preparedat elevatedtemperatures are
shown in Fig. 5(e) and (f). The lm deposited at 250 C shows an
increase in crystallite size when compared to the lm deposited at
room temperature. At a temperature of 500 C (Fig. 5(f)), large crystals
of Ni, in the size range of approximately 2070 nm, are embedded in a
TiN matrix that is the result of the increased mobility or diffusion of Ni
atoms during lm growth. This dynamic annealing encourages
the formation of larger Ni crystals than those observed at lower
temperatures.
Fig. 5. Pseudo colour EFTEM element maps of the lms deposited (a) in Ar and the lms
prepared in N
2
at (b) oating potential-room temperature, (c) 200 V bias-room
temperature, (d) 500 V bias-room temperature, (e) oating potential-250 C and (f)
oating potential-500 C. Ti is blue, N is red, Ni is green and the overlap of Ti and N is
displayed as pink.
Fig. 6. SEMimages of the lms deposited at (a) oating potential-roomtemperature in Ar
and the lms prepared inN
2
at (b) oating potential-roomtemperature, (c) 200 V bias-
roomtemperature, (d) 500 V bias-roomtemperature, (e) oating potential-250 C and
(f) oating potential-500 C.
398 A.M. Pagon et al. / Surface & Coatings Technology 235 (2013) 394400
3.5. Surface morphology
SEM images of the lms deposited at oating potential-room
temperature in Ar atmosphere (Fig. 6(a)) and N
2
atmosphere
(Fig. 6(b)) exhibit largely featureless surfaces. The RMS roughness
values for both of these lms, determined using AFM, was found to be
0.9 nm, a similar value to that obtained for the TiN lm. The addition
of a substrate bias of either 200 V (Fig. 6(c)) or 500 V (Fig. 6(d))
resulted in an increase in surface roughness to approximately 4.4 nm.
The change in surface morphology observed for the lms deposited
with an applied bias is consistent with the microstructure observed in
the TEM. The increase in surface roughness is also consistent with
increased sputtering at higher substrate bias, conrmed by the
reduction in deposition rate observed (Table 1).
The surface morphology of the lms deposited at oating potential,
with elevated substrate temperatures of 250 C and 500 C, are shown
in Fig. 6(e) and (f) respectively. The surface roughness increases to
3.3 nm for a deposition temperature of 250 C, due to the changes in
microstructure caused by dynamic annealing of the lmduring deposi-
tion. This effect is even more evident in the lm prepared at 500 C,
which exhibits a surface roughness of 8.9 nm, signicantly higher
than for all other lms and consistent with the porous microstructure
observed in the TEM.
3.6. Mechanical properties
The intrinsic stress of all the thin lms is shown in Table 3. The lm
deposited in Ar exhibited a low compressive stress of 0.6 GPa.
Under reactive deposition conditions in N
2
, the compressive stress was
the highest of all the TiN\Ni lm at oating potential-room
temperature with a value of 2.4 GPa. This increase in compressive
stress correlates with a microstructural change from a disordered
metallic lm to a ne scale nanocomposite TiN\Ni lm. As the applied
substrate bias was increased, there was a decrease in compressive stress
to 0.5 GPa for 200 V bias and 0.3 GPa for 500 V bias. This
decrease in compressive residual stress is again associated with further
changes in microstructure, in which there is clear resolution of Ni and
TiN phases and the Ni is now crystalline. This suggests that the crystal-
line Ni phase relieves internal stresses by plastic deformation. The
lms deposited at elevated temperature also exhibited changes in stress
when compared to the lm deposited at room temperature. At 250 C,
the lm exhibits a compressive stress of 0.7 GPa, similar to that
observed for the lm deposited at 200 V substrate bias and both
lms exhibit similar microstructures. When the substrate is heated to
500 C the highly porous microstructure leads to a change in residual
stress from compressive to tensile with a value of 0.5 GPa.
Loadunload curves for selected TiN\Ni thin lms and the TiN thin
lm are shown in Fig. 7. Variations of H and E* of the lms, shown in
Table 3, can be correlated to changes in microstructure. The lm
deposited in Ar exhibited an H of 7.4 GPa and E* of 130 GPa, while the
equivalent lm deposited in a N
2
atmosphere exhibited higher values
of 18.2 GPa and 210 GPa, respectively. Evidently, this increase in H and
E* is associated with the generation of the ne grain size of the ceramic
TiN phase. Clearly, the presence of the Ni phase modies H and E* of
the TiN since the equivalent TiN lm had an H of 32.0 GPa and E* of
260 GPa. The effect of substrate bias was a reduction in H to 14.3 GPa
at 200 V and 12.2 GPa at 500 V. This decrease in H is again
consistent with the changes in microstructure observed, that is, the
formation of crystalline Ni and the separation of the two phases TiN
and Ni.
Heating the substrate also caused a decrease in H to 13.9 GPa when
the substrate was substrate is heated to 250 C and a further decrease in
Hto 4.8 GPa whenthe substrate was heated to 500 C. E* also decreased
as the substrate temperature increased. The trend of decreasing H with
increase in temperature corresponds to an increase in the Ni crystallite
size. The lm microstructures generated at 200 V bias and at 250 C
yielded similar H and E* values while the large drop in H and E* for
the thin lm fabricated at 500 C is clearly related to the large crystals
of Ni and highly porous microstructure observed. The TiN\Ni nano-
composite lms prepared here exhibit higher hardness values
(maximum 17.0 GPa) than those previously reported for TiN\Ni thin
lms deposited by magnetron sputtering [18] (maximum 10.5 GPa).
The higher hardness values observed in this study are the result of
producing thin lms from the more energetic, 100% ionised plasma
generated in FCVA.
Table 3 shows W
e
for the lms. The TiNi thin lm exhibited a W
e
value of 44% in comparison to the TiN thin lm which exhibited the
highest W
e
of 75%. W
e
is lower for the TiN-Ni thin lm deposited at
oating potential-room temperature with a value of 65% showing that
the inclusion of a disordered Ni phase increases the ductility. An applied
substrate bias of 200 V decreased the W
e
to 53%, indicating that the
lm containing a crystalline phase of Ni is more ductile than one
containing a disordered phase of Ni. The lms deposited on heated
substrates showed W
e
values of 59% and 37% for lms deposited at
250 C and 500 C, respectively. This decrease in W
e,
corresponding to
andincrease inductility canbe explainedbythe increase inNi crystallite
sizes observed at elevated substrate temperatures.
Several authors [8,22] have used the ratio of H/E* as a way of
evaluating the endurance and toughness of a coating. These values are
shown in Table 3 and vary between 0.03 for the lm deposited at
500 C and the 0.12 for the TiN lm. Coatings which exhibit H/E* of
~0.1 or greater, along withW
e
higher than60%have beenfoundto resist
nucleation of cracking [7] and therefore are desirable when greater
toughness is required. The TiN lm satised criteria, and indeed no
Table 3
Summary the mechanical properties of the lms including Hardness (H), effective
modulus (E*), the ratio of H/E* and elastic recovery (W
e
).
Film
type
Bias (V) Temperature
(C)
Stress
(GPa)
H
(GPa)
E*
(GPa)
H/E* W
e
(%)
TiNi Floating Room temp. 0.6 7.4 130 0.06 44
TiN\Ni Floating Room temp. 2.4 18.2 210 0.09 65
TiN\Ni 200 Room temp. 0.5 14.3 220 0.07 53
TiN\Ni 500 Room temp. 0.3 12.2 180 0.07 56
TiN\Ni Floating 250 0.7 13.9 200 0.07 59
TiN\Ni Floating 500 0.5 4.8 150 0.03 37
TiN Floating Room temp. 6.4 32.0 260 0.12 75
Fig. 7. Representative loadunload curves for the lms deposited at (a) oating potential-
room temperature in Ar, the lms prepared in N
2
at (b) oating potential-room
temperature, (c) 500 V bias-room temperature, (d) oating potential-500 C and
e) the TiN lm.
399 A.M. Pagon et al. / Surface & Coatings Technology 235 (2013) 394400
cracking was observed around indentation sites when imaged either in
the scanning electron microscope or atomic force microscope. The
TiN\Ni lm deposited at oating potential also exhibits a W
e,
greater
than 60% along with a H/E* ratio of ~0.1 and a low intrinsic stress.
These attributes may make this lm a suitable candidate for use as a
grading layer in functionally graded coatings.
4. Conclusion
The effect of varying substrate bias (hence, deposition energy) and
deposition temperature of Ti\Ni/TiN\Ni nanocomposite thin lms
prepared using FCVA was investigated. Low roughness lms with ne
microstructure and a disordered Ni phase were observed when
depositedat roomtemperature in either Ar or N
2
atmosphere at oating
potential. An increase in bias or substrate temperature led to major
changes in microstructure, which in turn led to signicant changes
in properties of the TiN\Ni nanocomposites. An increase in the crystal-
linity of the Ni phase as well as larger TiN and Ni crystallite sizes were
observed with increasing substrate bias or temperature. At high bias,
there is a marked separation of the TiN and Ni phases resulting from
high levels of ion bombardment. All of the TiN\Ni thin lms exhibited
lower intrinsic stress, hardness and elastic recovery than a TiN lm
produced under similar conditions. The lm deposited at oating
potential was found to exhibit low compressive stress, while retaining
reasonable levels hardness and elastic recovery. This combination of
thin lm properties is potentially attractive for exploitation in metal
cutting applications, in particular as an interlayer between tool steel
and hard ceramic coating.
Acknowledgements
The authors acknowledge the facilities, and the scientic and
technical assistance, of the Australian Microscopy & Microanalysis
Research Facility at the RMIT Microscopy and Microanalysis Facility,
RMIT University. The authors also acknowledge the support of the
Australian Research Council and the CEO and Directors of Sutton Tools
Pty. Ltd.
References
[1] E.D. Doyle, Y.C. Wong, A.C. Vlasveld, Mater. Forum 22 (1998) 7995.
[2] S. Zhang, D. Sun, Y. Fu, H. Du, Surf. Coat. Technol. 198 (2005) 28.
[3] J. Musil, Surf. Coat. Technol. (2000) 322330.
[4] G.B. Gaitan, J.C. Caicedo, A.G. Balogh, S. Gottschalk, Phys. Status Solidi 4 (2007)
42604266.
[5] S. PalDey, S.C. Deevi, Mater. Sci. Eng. (2003) 5879.
[6] E.R. Weber, F. Fontaine, M. Scheib, W. Bock, Surf. Coat. Technol. 177 (2004)
227232.
[7] J. Musil, Surf. Coat. Technol. 207 (2012) 5065.
[8] J. Musil, F. Kunc, H. Zeman, H. Polakova, Surf. Coat. Technol. 154 (2002)
304313.
[9] Z. Yanhui, W. Xueqi, X. Jinquan, Y. Baohai, L. Fengqi, Applied Surface Science 258
(2011) 370376.
[10] C.K. Chung, H.C. Chang, S.C. Chang, M.W. Liao, Journal of Alloys and Compounds 537
(2012) 318322.
[11] P. Kuppusami, T. Elangovan, S. Murugesan, R. Thirumurugesan, S. Khan, R.P. George,
R. Ramaseshan, R. Divakar, E. Mohandas, D. Mangalaraj, Surface Engineering, 28
134-140.
[12] P. Kuppusami, R. Thirumurugesan, R. Divakar, S. Kataria, R. Ramaseshan, E.
Mohandas, J. Nanosci. Nanotechnol. 9 (2009) 55925595.
[13] J. Shi, A. Kumar, L. Zhang, X. Jiang, Z.L. Pei, J. Gong, C. Sun, Surface and Coatings Tech-
nology 206 (11-12) (2012) 29472953.
[14] J.-W. Lee, Z.-F. Zeng, C.-J. Wang, Adv. Mater. Res. 7982 (2009) 573576.
[15] S. Zhang, S. Deen, F. Yongqing, Y.T. Pei, J.T.M. De Hosson, Surf. Coat. Technol. 200
(2005) 15301534.
[16] J. Musil, P. Karvankova, J. Kasl, Surf. Coat. Technol. 139 (2001) 101109.
[17] J. Musil, F. Regent, J. Vac. Sci. Technol. A 16 (1998) 33013304.
[18] M. Misina, J. Musil, S. Kadlec, Surf. Coat. Technol. 110 (1998) 168172.
[19] F. Pinakidou, M. Katsikini, E.C. Paloura, A. Akbari, J.P. Riviere, Materials Science and
Engineering B: Solid-State Materials for Advanced Technology, 176 473-476.
[20] M. Irie, H. Ohara, M. Tsujioka, T. Nomura, Mater. Chem. Phys. 54 (1998) 317320.
[21] M. Irie, H. Ohara, A. Nakayama, N. Kitagawa, T. Nomura, Nucl. Instrum. Methods
Phys. Res., Sect. B 121 (1997) 133136.
[22] A. Leyland, A. Matthews, Wear 246 (2000) 111.
[23] A. Leyland, A. Matthews, Surf. Coat. Technol. 177178 (2004) 317324.
[24] A. Anders, Cathodic Arcs: From Fractal Spots to Energetic Condensation, Springer,
2008.
[25] N.B. Abaffy, J.G. Partridge, J. du Plessis, D.G. McCulloch, Phys. Status Solidi A 205
(2008) 14391442.
[26] G.G. Stoney, Proc. R. Soc. Lond. 82 (1909) 172175.
[27] W.C. Oliver, F.M. Pharr, J. Mater. Res. 7 (1992) 15641583.
[28] C. Kittel, Introduction to Solid State Physics, John Wiley & Sons, New York, 1986.
[29] J.L. He, K.W. Won, J.T. Chang, Thin Solid Films 359 (2000) 4654.
[30] L. Hultman, W.D. Munz, J. Musil, S. Kadlec, I. Petrov, J.E. Greene, J. Vac. Sci. Technol. A
9 (1991) 434438.
[31] G. Knuyt, C. Quaeyhaegens, J. D'Haen, L.M. Stals, Surf. Coat. Technol. 76 (1995)
311315.
[32] M.P. Seah, C.A. Clifford, F.M. Green, I.S. Gilmore, Surf. Interface Anal. 37 (2005)
444458.
400 A.M. Pagon et al. / Surface & Coatings Technology 235 (2013) 394400