Applied Surface Science 257 (2011) 7475–7480

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Deformation and fracture of TiN coating on a Si(1 1 1) substrate during

nanoindentation
T. An a,b , L.L. Wang a , H.W. Tian b , M. Wen b , W.T. Zheng b,∗
a
College of Science, Changchun University, Changchun 130022, PR China
b
Department of Materials Science, and Key Laboratory of Automobile Materials of MOE, Jilin University, Qianjin Street 2699, Changchun, Jilin 130012, PR China

a r t i c l e i n f o a b s t r a c t

Article history: The deformation mechanisms and fracture behavior of TiN coating on a Si(111) substrate, deposited
Received 10 September 2010 using magnetron sputtering Ti target, is characterized by nanoindentation experiments. The morpholo-
Received in revised form 6 March 2011 gies of the indentations are revealed by scanning electron microscopy, coupled with in situ atomic force
Accepted 7 March 2011
microscopy in nanoindentation experiments. The results show that permanent trigonal impressions and
Available online 12 March 2011
radial plastic grooves are confined within the contact regions even though the peak indenter displace-
ment increases to 1500 nm. Local cracks of TiN appear around the indent marks making the edges of
Keywords:
the indentations irregular. The cracks increase with an increase of the indenter displacement until the
TiN coating
Nanoindentation
indenter arrives at (or approaches) the Si(1 1 1) substrate at a critical displacement. As the peak indenter
Nanoscratch displacement increases to 2500 nm, an interfacial fracture between the TiN coating and the Si(1 1 1)
Cube corner indenter substrate is observed using both scanning electron microscopy micrograph and in situ atomic force
Radial crack microscopy images. The diameter of the interfacial fracture determined by scanning electron microscopy
Interfacial fracture micrographs is more accurate than that determined by in situ atomic force microscopy images in nanoin-
dentation experiments. The failure mechanism of the TiN coating is also investigated by means of a
standard nanoscratch test.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Hard thin films are usually used to enhance reliability and per-
formance of components in mechanical applications such as cutting
tools [1,2]. The enhancement gained by application of such thin
films can be neutralized by the high risk of crack formation through
the film or failure at the interface between the film and the sub-
strate. Contact-induced fracture in thin hard-film-coated systems
is complex and controlled by the coating material itself, by the
substrate upon which the coating is deposited and by the inter-
face which bonds the system together. Understanding the fracture
mechanisms and the sequence of fracture events during loading
and unloading is critical for understanding how the coated systems
will perform in service.
TiN has been widely applied as a protective coating on mechan-
ical tools. Recently, many studies have been performed to improve
the mechanical properties of TiN thin film through the growth of
nanocomposites [3,4] and multilayers [5–8]. Thus, the deformation
mechanism and fracture of TiN coating under contact became a very
important issue for the TiN-based nanocomposites and multilayer
coatings. A number of studies have been performed to evaluate
the fracture behavior of TiN coatings during indentation tests using
both spherical and sharp Vickers indenters [9–14]. Well-developed
radial cracks were observed extending far out of the residual indent
marks when the TiN coating on a Si substrate was indented by
spherical indenters [9]. Meanwhile, methods for deriving fracture
toughness from the indentation response have been modeled by
Weppelman et al. [9] for spherical indenter and by Loubet et al.
[13] for sharp Vickers indenter.
Harding et al. [15] have found that a cube corner indenter has a
sharper geometry than Vickers indenters, Berkovich indenters and
spherical indenters, and can reduce the cracking threshold. Thus,
the deformation and failure mechanism of a coating would be eval-
uated easily if a cube corner indenter is employed. In this paper,
we report the deformation mechanism and fracture of TiN coating
on a Si(1 1 1) substrate. Nanoindentation experiments were per-
formed using a cube corner indenter with tip end radius of 40 nm.
In order to compare the interfacial fracture induced by nanoinden-
tation with that induced by nanoscratch, a standard nanoscratch
test was also carried out with the same cube corner indenter.
2. Experimental

TiN coating was deposited using a JGP450A magnetron sput-

∗ Corresponding author. Tel.: +86 431 85168246; fax: +86 431 85168246. tering system, which had been described in detail elsewhere
E-mail address: WTZheng@jlu.edu.cn (W.T. Zheng). [16]. Ti (99.99%) was used as the target, placed on the direct

0169-4332/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2011.03.043
7476 T. An et al. / Applied Surface Science 257 (2011) 7475–7480

current cathode. The substrate Si(1 1 1) wafer with dimensions of

25 × 25 × 0.7 mm3 was ultrasonically cleaned in acetone, alcohol
and deionized water, and then mounted on the substrate holder.
During deposition, the whole gas pressure was kept at 0.8 Pa, in
which argon and nitrogen flow rate was fixed at 30.0 and 10.0 sccm,
respectively. Keeping substrate bias voltage and substrate temper-
ature at −80 V and 200 ◦ C, respectively, TiN coating with a thickness
of 1.2 ␮m was deposited.
The microstructure of the coating was investigated by X-ray
diffraction (XRD) using the Cu K␣ radiation at 1.5406 Å. The inden-
tation experiments were performed using MTS nanoindenter XP in
“displacement limit” mode, wherein indentations with peak dis-
placements ranging from 200 to 2500 nm were made using a cube
corner indenter under the condition that a strain rate is kept at
0.05/s. Scanning electron microscopy (SEM) measurements of the
indentations was performed using JEOL JSM-6700F. In situ atomic
force microscopy (AFM) measurements in nanoindentation experi-
ments were carried out to provide three-dimensional images of the
indentations.
A typical indentation experiment consists of four subsequent Fig. 2. SEM micrograph of the fractured TiN coating.
steps: loading segment at a fixed strain rate; holding segment at the
peak load for 10 s; unloading from peak load segment; and thermal
drift hold segment for 100 s at one tenth of the peak load. 3.2. Deformation and fracture behavior
Nanoscratch test was carried out at a maximum scratch load
of 100 mN, and the scratch length was 300 ␮m. A typical nano- Considerable insight into the behavior of coated systems can
scratch experiment consists of four subsequent steps: pre profile be gained from their load–displacement curves, especially when
segment for a length of 20% of the scratch length (i.e., 60 ␮m in a comparison is made with that of the substrate alone. The
this experiment) at a load of 0.1 mN; scratch profile segment for load–displacement curve of indentation made at 1500 nm peak
the scratch length; post profile segment for a length of 20% of the indenter displacement together with the SEM micrograph of the
scratch length (i.e., 60 ␮m in this experiment) at a load of 0.1 mN; indentation on Si(1 1 1) substrate is shown in Fig. 3. The curve is
and final profile segment for the whole length above (i.e., 420 ␮m
in this experiment) at a load of 0.1 mN.

3. Results and discussion

3.1. Structures

The microstructure of the TiN coating is disclosed by XRD pat-

tern in Fig. 1. The preferred orientation of the coating is (1 1 1) and
(2 2 2), and the average grain size, estimated by fitting the XRD
peaks using Pseudo-Voigt profile function, is 56.7 nm. The grains
are equiaxed as observed in the SEM micrograph of the fractured
coating (Fig. 2).

Fig. 3. Load–displacement curve (a) and SEM micrograph (b) of indentation made
Fig. 1. XRD pattern of the TiN coating. at 1500 nm peak indenter displacement on Si(1 1 1) substrate.
 T. An et al. / Applied Surface Science 257 (2011) 7475–7480 7477

Fig. 4. Load–displacement curves of indentations made at peak indenter displacements of (a) 200, (b) 800, (c) 1500 and (d) 2500 nm and the SEM micrographs of indentations
on TiN coating on the Si(1 1 1) substrate. Arrows in (c) and (d) indicate pop-ins during loading segment.

relatively smooth except that at the peak load of 14.09 mN during
holding load segment and at the minimum load of 1.40 mN during
thermal drift hold segment. There are two steps with lengths of 80
and 48 nm at the peak load and at the minimum load, respectively.
The step at the peak load is caused by an advance of the indenter
into the Si(1 1 1) substrate during holding load segment and the
step at the minimum load during thermal drift hold segment is due
to the recovery of the deformed substrate. The SEM micrograph
of the indentation exhibits well-developed radial cracks emanat-
ing at (or near) the indentation corners, and this can be attributed
7478 T. An et al. / Applied Surface Science 257 (2011) 7475–7480
to the wedge effect of the sharp cube corner indenter on the brit-
tle Si(1 1 1) substrate. Material is found tearing outside the indent
mark causing the edges of the residual indentation irregular. The
load–displacement curves made at peak indenter displacements
of 200, 800 and 2500 nm share the same characteristic with that
made at peak displacement of 1500 nm. The SEM micrographs of
the indentations also exhibit well-developed radial cracks emanat-
ing at the indentation corners and irregular chips on the surfaces of
the indent regions. The load–displacement curves and SEM micro-
graphs of the residual indentations show that the Si(1 1 1) substrate
reveals excellent capability of elastic recovery.
The load–displacement curves of indentations made at 200, 800,
1500 and 2500 nm peak indenter displacements together with the
SEM micrographs of indentations on TiN coating on the Si(1 1 1)
substrate are shown in Fig. 4. The loading curves made at 200 and
800 nm are parabolic and the unloading segments display little
elastic recovery compared to that made on the Si(1 1 1) substrate
alone. The micrograph shows a permanent trigonal impression at
the indentation centre and three radial plastic grooves are con-
fined within the contact region. Well-developed radical cracks,
observed previously using spherical indenters [9], cannot be found
at magnifications up to 20,000 and 40,000×. The shape of the inden-
tations implies that, during loading, the coating/substrate system
is flexed and bent to make sufficiently forceful contact with the
three edges of the indenter so as to leave permanent (plastically
deformed) grooves. Lips of material are found overhanging on
the edges of the indentations and they increase with an increase
of indenter displacement. When the peak indenter displacement
increases to 1500 and 2500 nm, a slight pop-in at a displacement
of about 1000 nm appears in the loading segment (Fig. 4c and d).
This may be due to the fracture of the Si(1 1 1) substrate or other
fractures underneath the coating surface (e.g., interfacial fracture).
The unloading segment of the curve made at peak displacement of
1500 nm is relatively smooth but that made at peak displacement
of 2500 nm shows a large step of about 184 nm during the thermal
drift hold segment. The indentation made at peak displacement
of 1500 nm is more regular with less lips of material overhang-
ing on the edges of the indent mark than those made at peak
displacements of 200 and 800 nm. However, as the peak indenter
displacement increases to 2500 nm, a large area of TiN coating is
peeled off completely from the Si(1 1 1) substrate and the coating
shows a annular fractured topography around the residual indent
mark (Fig. 4d). This denotes that interfacial fracture between TiN
coating and the Si(1 1 1) substrate takes place as the peak indenter
displacement reaches 2500 nm. The residual indent mark on the
coating-peeled Si(1 1 1) substrate shows radial cracks again, but the
indentation centre does not show any trigonal impression (Fig. 5).
This implies that it is the TiN coating underneath the indenter but
not the indenter itself which is pressed into the Si(1 1 1) substrate
causing the fracture of the Si(1 1 1) substrate.
To further understand the deformation mechanism of the TiN
coating on the Si(1 1 1) substrate, another series of indentations
are performed and in situ AFM measurements in nanoindentation
experiments are carried out for the indentations with peak inden-
ter displacements of 800, 1500 and 2500 nm. In order to observe
the contact region clearly, the scale perpendicular to the coating
surface in AFM images is enlarged by 200 times. Fig. 6 displays the
top view and cross-sectional images for the three indentations. The
edges of the indentation made at 800 nm peak indenter displace-
ment are not sharp but irregular with pile-ups locating around the
residual indentation. The pile-ups are confined in the local area
around the indent mark and the height for the pile-ups is about
82 nm. As the peak indenter displacement increases to 1500 nm,
the edges of the indentation are regular and the height for the
pile-ups around the indentation is 60 nm, which is shorter than
that produced at peak displacement of 800 nm. This is in agree-
Fig. 5. SEM micrograph of the residual indent mark on coating-peeled Si(1 1 1)
substrate.
ment with the SEM observations and it can be explained as follows:
at lower peak indenter displacement, the energy induced by the
sharp cube corner indenter is relaxed by producing local cracks,
which leads to the local pile-ups around the residual indentation.
However, as the peak indenter displacement increases to a critical
value and the indenter arrives at (or approaches) the Si(1 1 1) sub-
strate, the fracture of the Si(1 1 1) substrate or other cracks such
as interfacial fracture between TiN coating and the Si(1 1 1) sub-
strate may occur, and these fractures become the main approach
to relax the strain energy induced by the indenter. The fracture
of the Si(1 1 1) substrate and the interfacial fracture between TiN
coating and the Si(1 1 1) substrate can help to reduce the local
cracks around the indentation. As the peak indenter displacement
increases to 2500 nm, a blister with a diameter of 24 ␮m can be
found in the top view image (Fig. 6c), and this blister is an evi-
dence of interfacial fracture between TiN coating and the Si(1 1 1)
substrate. The height of the blister reaches 300 nm and the brim is
far from the indentation centre. The interfacial fracture mechanism
for a ceramic coating on a Si substrate was mentioned elsewhere
[17], and it can be explained as follows: during loading, the coat-
ing underneath the indenter is pressed into the impression in the
plastically deformed substrate, which causes a compressive stress
at the contact region, making the coating remain pressed against
the substrate. However, during unloading, the coating is detached
from the substrate and behaves like a spring, pushing the indenter
out of the impression and generating an extra load at lower depths
than normal elastic unloading. This is why a large blister around the
indentation and a large step during the thermal drift hold segment
appear as the peak displacement reaches 2500 nm.
It should be noted that the in situ AFM images shows a diameter
of 24 ␮m for the interfacial fracture when the peak indenter dis-
placement is 2500 nm, whereas the SEM micrograph exhibits that
the diameter of the interfacial fracture is about 50 ␮m. To evalu-
ate this difference, another indentation experiment is performed
at a peak indenter displacement of 2500 nm, but the strain rate is
fixed at of 0.2/s. Fig. 7 shows the top view in situ AFM image of the
indentation. Half of a blister with a diameter of 25 ␮m is observed
in the image. However, the TiN coating composing the other half
of the blister is peeled off, leaving a fan-like cracked topography
with a diameter of 50 ␮m. This implies that the diameter of the
blister is not exact the diameter of the interfacial fracture between
TiN coating and the Si(1 1 1) substrate, and the SEM observation is
a accurate means for evaluating interfacial fractures.
 T. An et al. / Applied Surface Science 257 (2011) 7475–7480 7479

Fig. 6. In situ AFM images for indentations made at peak indenter displacements of (a) 800 nm, (b) 1500 nm and (c) 2500 nm on TiN coating on the Si(1 1 1) substrate.

Fig. 8 shows the penetration curves and applied load as a func-
tion of scratch distance. The corresponding optical image of the
scratch damage is shown in Fig. 9. During the scratch profile seg-
ment, a large valley can be seen as indicating the interfacial fracture
between TiN coating and the Si(1 1 1) substrate. The critical load
for the interfacial fracture can be determined as 65.56 mN, and this
value is approximatively equal to those observed in nanoindenta-
tion experiments as slight pop-ins in loading curves when the peak
indenter displacement reaches 1500 and 2500 nm. This means that
the critical load for interfacial fracture can be determined by either
nanoindentation experiment or nanoscratch test. With a further
increase of scratch distance and applied load, interfacial fracture
expands along the scratching direction because valleys increase in
the scratch profile. During the final profile segment, the penetration
7480 T. An et al. / Applied Surface Science 257 (2011) 7475–7480
Fig. 7. In situ AFM image for indentation made at peak indenter displacement of
2500 nm but with a strain rate of 0.2/s.
Fig. 8. Penetration curves and applied load as a function of scratch distance.
depth is shallower than that in the scratch profile segment when the
scratch distance is below 173 nm, and this is caused by the recov-
ery of the deformed coating after the scratch profile segment. As the
scratch distance exceeds 173 nm, a sudden jump of scratch depth
can be seen, and this jump can be attributed to another interfacial
fracture at the fixed load of 0.1 mN. This means that when the coat-
ing is scratched previously at a relative large force, an interfacial
fracture can be produced easily at a relative small force. The high
jump at a scratch distance of about 300 nm is due to large fractured
chips which causing the indenter out of the scratch grooves.
Fig. 9. Optical image of the scratch damage of TiN coating on Si(1 1 1) substrate.
4. Conclusions
The deformation mechanisms and fracture behavior of TiN
coating deposited on a Si(1 1 1) substrate is characterized by
nanoindentation experiments. It is found that, as the peak indenter
displacement is below 1500 nm, no well-developed radial cracks
are found. The trigonal impressions and plastic grooves in TiN
coating are confined within the contact regions around which
local cracks take place. However, when the peak indenter dis-
placement increases to 2500 nm, an interfacial fracture between
the TiN coating and the Si(1 1 1) substrate occurs as observed
by SEM micrograph and in situ AFM images. The diameter of
the interfacial fracture determined by SEM micrographs is more
accurate than that determined by in situ AFM images in nanoin-
dentation experiments. The interfacial fracture mechanism can be
investigated by either nanoindentation experiment or nanoscratch
test.
Acknowledgements
Support from National Natural Science Foundation of
China (Grant No. 50832001), the special PhD program (Grant
No. 200801830025) from MOE, “973” project (Grant No.
2010CB631001) from MOST, the “211” and “985” project of
Jilin University, and Fundamental Research Fund of Jilin University
(Grant No. 421060272467) are highly appreciated.
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