Thin Solid Films 315 Ž1998.

214–221

Measurement of fracture toughness of ultra-thin amorphous carbon films

)
Xiaodong Li, Bharat Bhushan
Computer Microtribology and Contamination Laboratory, Department of Mechanical Engineering, The Ohio State UniÕersity,
Columbus, OH 43210-1107, USA
Received 8 May 1997; accepted 16 September 1997

Abstract

The nanoindentation fracture of ultra thin amorphous carbon films on silicon by a conical indenter was studied, and compared with the
nanoindentation fracture of the same films on silicon by a cube corner indenter. It is found that the conical indenter gives an indentation
fracture similar to that by the cube corner indenter. The cube corner indenter results in a larger stress concentration leading to fracture of
films at lower loads. Based on the analysis of the energy release in cracking, the fracture toughness of the films was calculated. The
results show that the conical indenter gives the same fracture toughness values as the cube corner indenter and these calculated values are
in good agreement with those measured by conventional methods. q 1998 Elsevier Science S.A.

Keywords: Fracture toughness; Nanoindentation; Energy release; Amorphous carbon films

1. Introduction ally found to be slightly higher. Although cracking thresh-

olds can be reduced down to 5 mN w5x by using a cube
The successful performance and reliability of thin films
corner indenter, the corresponding indentation depth Žabout
is often limited by their mechanical properties. Among the
250 nm for most brittle materials. exceeds 10% thickness
mechanical properties of interest, hardness, elastic modu-
of ultra-thin films Žon the order of 10 nm thickness. and
lus and fracture toughness are measured using indentation
the elastic-plastic zone may expand to the substrate. For
methods w1–4x. Although nanoindentation methods are used
these cases, conventional fracture toughness measurement
routinely in characterization of the elastic modulus and
based on the radial cracking cannot be used. Furthermore,
hardness of thin films, the development of measuring
at shallow indentation depths, it is difficult to measure
fracture toughness of thin films lags far behind. Conven-
radial crack length under scanning electron microscope
tional fracture toughness measurement is based on the
ŽSEM.. Therefore, it is necessary to find other methods to
radial cracking which occurs when brittle materials are
measure fracture toughness of ultra-thin films.
indented by a sharp indenter. The length of radial cracks is
Load-displacement studies in nanoscale indentation of
known to correlate with the fracture toughness and is used
films have been conducted by various researchers Že.g.,
to calculate fracture toughness w2,3x. However, a problem
w4,6–8x.. The indentation fracture mechanics of brittle
is encountered in extending the method into the nanoinden-
materials by Vickers and Berkovich indenters have been
tation regime in that there are well defined loads, called
widely studied for many years. In an earlier study, a
cracking thresholds, below which indentation cracking does
technique to measure fracture toughness of thin films using
not occur in most brittle materials. For a Vickers indenter
a cube corner indenter has been developed w9x. In the
which is widely used in microindentation experiments,
present paper, a conical indenter was used. On the basis of
cracking thresholds in most ceramics are about 0.25 N or
understanding of the nanoindentation fracture of silicon,
more, i.e., loads well above those which would normally
fracture mechanisms of amorphous carbon films on silicon
be used in nanoindentation. The thresholds for a Berkovich
in nanoindentation were studied. The fracture toughness of
indenter Žroutinely used in nanoindentation experiments
these films was calculated using the methodology estab-
for measuring hardness and elastic modulus. were gener-
lished by the cube corner indenter and compared with the
fracture toughness obtained by the nanoindentation using
)
Corresponding author. the conical indenter.

0040-6090r98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

PII S 0 0 4 0 - 6 0 9 0 Ž 9 7 . 0 0 7 8 8 - 8
 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221 215

2. Experimental
Amorphous carbon films of 400 nm thickness were
deposited on polished Ž100. single-crystal silicon substrate
Žrms surface roughness 2–3 nm. by cathodic arc and ion
beam deposition techniques w8x. The kinetic energies for
cathodic arc deposition and ion beam deposition are 100–
2500 and 50–500 eV, respectively. Nanoindentations as a
function of load were made using a commercially available
instrument. This instrument monitors and records the dy-
namic load and displacement of the indenter during inden-
tation with a force resolution of about 75 nN and displace-
ment resolution of about 0.1 nm w4x. A conical indenter
with an included angle of 908 and a tip radius of 0.1 m m
were used. In order to compare with the nanoindentation
fracture of the same films on silicon by the cube corner
indenter, the same indentation experiment as used in our
previous work w9x was used: approached the surface; loaded
to peak load over 10 s; held the indenter at peak load for
10 s; and unloaded completely. Indentations and associated
crack patterns were observed using SEM.
3. Results
3.1. Silicon
The load-displacement curves of indentations made at
10, 30 and 100 mN peak indentation loads using the
conical indenter and corresponding SEM micrographs of
indentations on silicon are shown in Fig. 1. The load-dis-
placement curves of indentation made at 10 and 30 mN are
smooth. SEM micrographs show that at 10 mN peak
indentation load no cracks are observed except the residual

Fig. 1. Load-displacement curves of indentations made at 10, 30 and 100 mN peak indentation loads using the conical indenter Ža. and the SEM
micrographs of indentations Žb. on silicon. Arrow indicates discontinuity during unloading portion of the curve.
216 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221

Fig. 2. Load-displacement curves of indentations made at 20 and 30 mN peak indentation loads using conical indenter Ža. and the SEM micrographs of
indentations Žb. on the ion beam carbon film on silicon. Arrow indicates a step during loading portion of the load-displacement curve.

Fig. 3. Load-displacement curves of indentations made at 20 and 22.5 mN peak indentation loads using the cube corner indenter Ža. and the SEM
micrographs of indentations Žb. on the ion beam carbon film on silicon. Arrow indicate a step during loading portion of the load-displacement curve w9x.
 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221
indent mark. At 30 mN peak indentation load, four radial
cracks were generated, emanating along preferred direc-
tions. Armstrong et al. w10x observed the same phe-
nomenon and suggested that the preferred directions are
the ²112: directions in silicon. The load-displacement
curve of indentation made at 100 mN peak indentation
load, exhibits several short displacement discontinuities
during the loading step and a discontinuity in the unload-
ing curve. In addition to the four radial cracks having
propagated, the tearing of material outside the indent re-
gion and significant delamination are observed in the 100
mN SEM micrograph. This indicates that lateral cracking
occurred during unloading, which is believed to be associ-
ated with the discontinuity in displacement during unload-
ing w11x.
Compared with the nanoindentations made on silicon
using a cube corner indenter w9x, it is noted that at the same
peak indentation load, the cube corner indenter gives higher
indentation depth and exhibits much lower radial and
lateral cracking threshold loads than the conical indenter.
This indicates that the cube corner indenter penetrates into
the material easier than the conical indenter at a given
load. This suggests that cube corner indenter results in a
larger stress concentration leading to the radial and lateral
cracking than the conical indenter. For both indenters,
however, the indentation depths at the radial cracking
threshold loads exceed the 10% thickness of ultra-thin
films on the order 10 nm in thickness.
Fig. 4. Load-displacement curves of indentations made at 30 and 350 mN peak indentation loads using conical indenter Ža. and the SEM micrographs of
indentations Žb. on the cathodic arc carbon film on silicon. Arrow indicates a step during loading portion of the load-displacement curve.
217
3.2. Amorphous carbon films on silicon substrate
The load-displacement curves of indentations made at
20 and 30 mN peak indentation loads using the conical
indenter together with the SEM micrographs of indenta-
tions on the ion beam carbon film on silicon are shown in
Fig. 2. The load-displacement curve of indentation made at
20 mN peak indentation load is smooth whereas that made
at 30 mN peak indentation load exhibits a step in the
loading curve. The 20 mN SEM micrograph shows that in
addition to several radial cracks, ring-like through-thick-
ness cracking is observed with the film around the indenter
overhanging the edge of the indentation. Also we note that
the film around the indenter has bulged upwards, indicat-
ing delamination and buckling. Since no steps are observed
in the loading curve of indentation made at 20 mN peak
indentation load, it is believed that the film under the
indenter was not separated instantaneously from the bulk
film via the ring-like through-thickness cracking but oc-
curred over a period of time w9x. At 30 mN peak indenta-
tion load, partial ring-like spalling is observed around the
indenter and the other parts of the film have bulged
upwards as shown in Fig. 2b. This partial ring-like spalling
is believed to result in the step in the loading curve.
Comparison of the data obtained using the cube corner
indenter shown in Fig. 3 w9x, shows a good correspondence
between the step in the loading curve and morphology of
ring-like through-thickness cracking and spalling.
218 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221

The load-displacement curves of indentations made at
30 and 350 mN indentation loads using the conical inden-
ter together with the SEM micrographs of indentations on
the cathodic arc carbon film on silicon are shown in Fig. 4.
At 30 mN peak indentation load, a step is present at about
20 mN in the loading curve and correspondingly a ring-like
through-thickness cracking is observed. No interface cracks
are found on the indentation surface. The film around the
indenter has not bulged upwards. This observation sug-
gests that no delamination and buckling occurred. There-
fore, it is believed that this step results from the ring-like
through-thickness cracking and not from interfacial crack-
ing. We note that the radius of the ring-like crack is equal
to the contact radius between the indenter and the film at
the indentation depth at which the step started to occur in
the loading curve. This indicates that the ring-like
through-thickness cracking occurred at the contact edges.
At the peak indentation loads up to 350 mN Žlimit load of
the nanoindenter., radial cracking, delamination and buck-
ling are observed without spalling. No steps are observed
in the corresponding loading curves. The four radial cracks
which occurred along the preferred directions are believed
to result from the silicon substrate and not from the film.
The lateral cracks which formed in the silicon substrate are
clearly observed, which is believed to be associated with
the discontinuity in displacement in the unloading curve
w11x. For the data obtained using the cube corner indenter
w9x, steps are found in the loading curves of indentations
made at 30, 100 and 200 mN peak indentation loads as
shown by arrows in Fig. 5a. The 30 mN SEM micrograph

Fig. 5. Load-displacement curves of indentations made at 30, 100 and 200 mN peak indentation loads using the cube corner indenter Ža. and the SEM
micrographs of indentations Žb. on the cathodic arc carbon film on silicon. Arrows indicate steps during loading portion of the load-displacement curve w9x.
 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221
shows ring-like through-thickness cracking with small lips
of material overhanging the edge of the indentation. The
steps at about 23 mN in the loading curves of indentations
made at 30 and 100 mN peak indentation loads are be-
lieved to result from this ring-like through-thickness crack-
ing. The step at 175 mN in the loading curve of indenta-
tion made at 200 mN peak indentation load is caused by
spalling, which cannot be found at the peak indentation
loads up to 350 mN using the conical indenter.
Comparison of Figs. 2–5 shows that the cube corner
and conical indenters give similar nanoindentation fracture
for the films used in this study. The cube corner indenter
has lower critical loads for ring-like through-thickness
cracking and spalling than the conical indenter. This sug-
gests that the cube corner indenter results in a larger stress
concentration leading to fracture of films at lower loads. In
addition to the difference between the stress distributions
caused by the cube corner and conical indenters, the edges
of the cube corner indenter cut through the films during
indentation, making the fracture of the films much easier
than the conical indenter.
4. Analysis and discussion
It is found from Fig. 1a that for the silicon substrate,
there are not any long steps in the loading curves except
several short discontinuities. The same result was obtained
in the case of using the cube corner indenter w9x. This
suggests that the steps in the loading curves of indentations
made on the films in Figs. 2–5, result from the film and
not from the substrate. The cube corner and conical inden-
ter give similar indentation fracture of the films. As we
established in our previous work w9x, fracture process
progresses in three stages: Ž1. first ring-like through-thick-
ness cracks form around the indenter by high stresses in
the contact area, Ž2. delamination and buckling occur
around contact area at the filmrsubstrate interface by high
lateral pressure, Ž3. second ring-like through-thickness
cracks and spalling are generated by high bending stresses
at the edges of the buckled film, see Fig. 6. In the first
stage, if the film under the indenter is separated from the
bulk film via the first ring-like through-thickness cracking,
a corresponding step will be present in the loading curve.
If discontinuous cracks form and the film under the inden-
ter is not separated from the remaining film, no step
appears in the loading curve because the film still supports
the indenter and the indenter cannot suddenly advance into
the material. In the second stage, for the films used in the
present study, the advances of the indenter during the
radial cracking, delamination and buckling are not big
enough to form steps in the loading curve because the film
around the indenter still supports the indenter, but generate
discontinuities which change the slope of the loading curve
with increasing indentation loads. In the third stage, the
219
Fig. 6. Schematic of various stages in nanoindentation fracture for the
filmrsubstrate system.
stress concentration at the end of the interfacial crack
cannot be relaxed by the propagation of the interfacial
crack. With an increase in indentation depth, the height of
the bulged film increases. When the height reaches a
critical value, the bending stresses caused by the bulged
film around the indenter will result in the second ring-like
through-thickness crack formation and spalling at the edge
of the buckled film as shown in Fig. 6, which leads to a
step in the loading curve. This is a single event and results
in the separation of the part of the film around the indenter
from the bulk film via cracking through films. The step in
the loading curve is totally from the film cracking and not
from the interfacial cracking or the substrate cracking.
It is well known that the area under the load-displace-
ment curve is the work performed by the indenter during
elastic-plastic deformation of the filmrsubstrate system.
The strain energy release in the firstrsecond ring-like
cracking and spalling can be calculated from the corre-
sponding steps in the loading curve. Fig. 7 shows a
modeled load-displacement curve. OACD is the loading
curve. DE is the unloading curve. Since the first ring-like
through-thickness cracking does not always lead to a step
in the loading curve in some films like the ion beam
carbon film used in this study ŽFig. 2a and Fig. 3a., the
second ring-like through-thickness crack should be consid-
ered. It should be emphasized that the edge of the buckled
film is far from the indenter, therefore, it does not matter if
the indentation depth exceeds the film thickness or if
deformation of the substrate occurs around the indenter
when we measure fracture toughness of the film from the
220 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221

extrapolated along the tangential direction of the loading

Fig. 7. Schematic of a load-displacement curve, showing a step during the
loading cycle and associated energy release.
released energy during the second ring-like through-thick-
ness cracking Žspalling.. Suppose that the second ring-like
through-thickness cracking occurs at AC. Now, let us
consider the loading curve OAC. If the second ring-like
through-thickness crack does not occur, it can be under-
stood that OA will be extended to OB to reach the same
displacement as OC. This means that the crack formation
changes the loading curve OAB into OAC. For point B,
the elastic-plastic energy stored in the filmrsubstrate sys-
tem should be OBF. For point C,the elastic-plastic energy
stored in the filmrsubstrate system should be OACF.
Therefore, the energy difference before and after the crack
generation is the area of ABC, i.e., this energy stored in
ABC will be released as strain energy to create the ring-like
through-thickness crack. According to the theoretical anal-
ysis in our previous work w9x, the fracture toughness of thin
films can be written as
1r2
E U
K IC s
ž Ž 1 y n 2 . 2p C R /ž /
t
Ž 1.
where E is the elastic modulus, n is the Poisson’s ratio,
2p C R is the crack length in the film plane, U the strain
energy difference before and after cracking, and t is the
film thickness.
Based on Eq. Ž1., the fracture toughness of both films
has been calculated. U is assessed from the steps in Fig.
2a, Fig. 3a and Fig. 5a at the peak indentation loads of 30,
22.5 and 200 mN, respectively. The loading curve is
curve from the starting point of the step up to reach the
same displacement as the step. The area between the
extrapolated line and the step is the estimated strain energy
difference before and after cracking. C R is measured from
SEM micrographs in Fig. 2b, Fig. 3b and Fig. 5b. Second
ring-like crack is where the spalling occurs. The calculated
fracture toughness values are shown in Table 1. For the
data obtained using the conical indenter, the calculated
fracture toughness value for the ion beam carbon film on
silicon is 5.4 MPa6m. In the case of using the cube corner
indenter, the calculated fracture toughness values are 4.9
MPa6m for the ion beam carbon film on silicon and 10.9
MPa6m for the cathodic arc carbon film on silicon. The
conical and cube corner indenters give very close fracture
toughness values. These calculated fracture toughness val-
ues for both amorphous carbon films in this study are
comparable with the fracture toughness of diamond Ž3–11
MPa6m. or diamond films Ž5–6 MPa6m. w12x and other
ceramic coatings w13x measured by a well known radial
crack technique.
A higher deposition kinetic energy will result in a larger
fraction of sp 3-bonded carbon in amorphous network w8x.
The sp 3-bonded carbon exhibits the outstanding properties
of diamond w8x. Thus, the higher kinetic energy for the
cathodic arc deposition could be one of the possible rea-
sons why the cathodic arc carbon film exhibits a higher
fracture toughness value than the ion beam carbon film.
Next, we discuss the effect of residual stresses on the
fracture toughness measurement. We assume that the resid-
ual stresses are distributed uniformly in the film and the
film has a homogeneous structure. In the second stage of
the fracture process, the compressive stresses on the film
surface and the tensile stresses on the bottom of the film
produced by indentation are basically equal. Therefore,
before the third stage, the elastic strain energy stored in the
film produced by indentation process should not be af-
fected by the residual stresses in the film. Since the energy
release in cracking comes from the stored elastic strain
energy, the fracture toughness value measured by this
methodology should not be affected by the residual stresses
in the films. However, the residual stresses will affect the
fracture toughness of the film having a heterogeneous
structure andror non-uniformly distributed residual
stresses. For this kind of film, the effect of residual
stresses on fracture toughness is more complex and needs
further study.

Table 1
Mechanical properties of cathodic arc and ion beam carbon films
Film Indenter t Ž m m. Peak indentation load ŽmN. E ŽGPa. n U ŽnNm. C R Ž m m. K IC ŽMPa6m.
Ion beam conical 0.4 30 150 0.25 2.4 4.6 5.4
Ion beam cube corner 0.4 22.5 150 0.25 1.6 4.0 4.9
Cathodic arc cube corner 0.4 200 300 0.25 7.1 7.0 10.9
 X. Li, B. Bhushanr Thin Solid Films 315 (1998) 214–221
5. Conclusions
The nanoindentation fracture of amorphous carbon films
by the conical indenter was studied. Good correspondence
between a step in the loading curve and morphology of
ring-like cracking and spalling was found. Comparison of
the nanoindentation fracture of the films by the conical and
cube corner indenters shows that the conical and cube
corner indenters give similar fracture process. The fracture
toughness of the films were calculated from the steps in
the loading curves in terms of the energy release in
cracking. The results show that the cathodic arc carbon
film has a higher fracture toughness than the ion bean
carbon film. Compared with the conical indenter, the cube
corner indenter is recommended to be used for measure-
ment of fracture toughness of hard thin films because of
lower contact area, it results in lower critical load for
ring-like through-thickness cracking and spalling.
Acknowledgements
The authors would like to thank John C. Mitchell for
assistance with SEM. The research was supported by the
Office of Naval Research, Department of Navy ŽContract
No. N00014-96-1-10292.. The content of the information
does not necessarily reflect the position or policy of the
Government, and no official endorsement should be in-
ferred.
221
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