Wear 243 (2000) 85–91

Analysis of cracking induced by scratching of

tungsten coatings on polyimide substrate
J. Ligot, S. Benayoun∗ , J.J. Hantzpergue
Laboratoire Procédés Matériaux Instrumentation, ENSAM-CER d’Angers, 2 Bd du Ronceray, BP 3525, 49035 Angers, France
Received 25 October 1999; received in revised form 19 April 2000; accepted 19 May 2000

Abstract
Tungsten films were deposited on Upilex S polyimide substrates using a triode discharge system. Films 200, 400 and 600 nm thick were
produced at three different argon deposition pressures (0.2, 0.7 and 1.2 Pa). The behaviour of the metallic coating–polymeric substrate
composite was studied by sliding indentation. Three different scratching tests were carried out: in increasing load mode (ILM), in increasing
load mode with multipass (ILM-M), and in constant load mode (CLM). These scratchings induced transversal crack formation but no
coating delamination in the range of the studied parameters (applied load L≤30 N, load gradient≤15 N mm−1 ). The critical load, Lic was
defined as the load at which cracks occurred in the coating homogeneously throughout the scratch. The superscript i denotes the number
of scratches in multipass mode.
Intrinsic parameters such as scratching speed (dx/dt) or loading rate (dL/dt) were considered in order to facilitate the interpretation of
the critical load results. It was shown that L1c (in ILM) increased with deformation rate of the polyimide substrate. Qualitative assessments
of the coating toughness under sliding indentation were proposed by the comparison of L1c and L10 c (in ILM-M). Comparative information
about the size and the length distribution of pre-existing cracks within the tungsten coatings were obtained by interpreting the CLM results.
© 2000 Elsevier Science S.A. All rights reserved.
Keywords: Scratch test; Tungsten; Coating; Polyimide; Fracture

1. Introduction different scratch modes (increasing load mode and con-

Metallization of polymer substrates is widely used in var-
ious industrial applications. Many studies reported the tech-
nological importance of multilayer devices (metal/polymer)
in microelectronics and the properties of these devices
such as adhesion or electrical resistivity required for these
applications [1,2]. In packaging, decorative applications,
or electromagnetic insulation the coatings can be exposed
to mechanical stresses, especially scratches. In the last 10
years, scratch tests on metallic coatings and polymeric
substrates have been performed. These studies were gen-
erally focused on the characterization of the film–substrate
adhesion [3–5]. The aim of this study is given.
• Firstly, to show that tungsten metal coating can adhere to
polyimide substrate.
• Secondly, to evaluate damages induced by scratches with
regard to the influence of the intrinsic scratch parameters
(loading rate or scratching speed) and with regard to the
∗ Corresponding author. Tel.: +33-2-41-20-73-87;
fax: +33-2-41-20-73-87.
E-mail address: stephane.benayoun@angers.ensam.fr (S. Benayoun).
stant load mode).
• Thirdly, to analyse the results in order to obtain a qualita-
tive characterization of the toughness and the microstruc-
ture of the tungsten coatings.
2. Experimental procedure
2.1. Deposition of metal films
Tungsten films were deposited on Upilex S polyimide
and Si single crystal substrates. Before introduction into
the sputtering chamber, a solvent wet cleaning (ethanol
and de-ionized water) of the substrates was carried out in
ultrasonic bath and was followed by nitrogen drying. The
polyimide samples were then annealed at 200◦ C for 2 h, in
order to evaporate alcohol and water absorbed by the poly-
mer. Si wafers (15 mm×10 mm) were placed side by side
with polyimide substrates (15 mm×15 mm) on the substrate
holder.
The W films were deposited using a triode discharge
system (Trion 400 Alcatel) with pure argon as sputtering

0043-1648/00/$ – see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 0 4 3 - 1 6 4 8 ( 0 0 ) 0 0 4 2 1 - X
86 J. Ligot et al. / Wear 243 (2000) 85–91
gas. The main advantage of the triode discharge lies in the
possibility to independently control sputtering parameters,
such as argon pressure, target current and accelerating volt-
age for the Ar+ ions. Filament, positively biased anode and
magnetic coil generate a plasma actually independent of the
target and substrate voltages.
The cylindrical chamber was 360 mm in diameter and
310 mm in length. This deposition chamber included two
water-cooled target holders (target diameter=100 mm). The
distance between substrate holder and W target (purity:
99.96%) was 120 mm. The substrate temperature was mea-
sured during sputtering with a thermocouple in contact with
the substrate side on the substrate holder.
The base pressure in the sputtering chamber was larger
than 2×10−4 Pa for all the depositions. W films were
deposited with different argon pressures: 0.2, 0.7 and 1.2 Pa.
The target voltage was fixed at −1100 V and the target cur-
rent varied from 75 to 115 mA, according to the working
pressures. Prior to any deposition the target surface was
sputter-cleaned for 30 min, while the substrates were pro-
tected by a screen. The substrate temperature was always
estimated below 55◦ C.
2.2. Characterization
As the roughness of the polyimide substrate (Ra) was
about 1 ␮m, the thickness of the W layers was preferably
determined on Si substrate by Talystep profilometer mea-
surements. Previous studies showed that no mass loss was
observed between W films deposited on PI and W film de-
posited on Si [6]. A screen formed by a very thin microscope
slide was placed on the Si wafer before deposition. After de-
position a steep step of tungsten was formed on the boarder
of the slide. Thickness of the W film was determined by
the step height measurement. Three film thicknesses were
achieved: 200, 400 and 600 nm.
Fig. 1. Optical micrograph of the crack pattern within the track. Film thickness was 200 nm, the deposition pressure 1.2 Pa and the load gradient 15 N mm−1 .
Scratches were produced with a Micro Scratch Tester
(MST-CSEMEX) equipped with a Rockwell C diamond sty-
lus (conical angle, 120◦ ; tip radius, 200 ␮m) and a tangential
force sensor. The test consisted of applying an incrementally
or linearly increasing load on the sample surface through the
indenter in order to damage the surface by scratching. The
scratch was then observed by optical microscopy.
The tungsten coatings were firstly tested with a linearly
increasing load mode (ILM). Multipass tests (ILM-M) in the
same mode at fixed parameters were secondly carried out to
study the behaviour of the coatings during this damage. The
W coatings were thirdly tested in constant load mode (CLM)
from the number of cracks generated within the scratch track.
3. Results and discussion
3.1. Optical observation of the cracks
The critical load, L1c , was determined by optical observa-
tions. L1c was defined as being the load corresponding to the
creation of the first crack in increasing load mode (ILM). An
optical micrograph of the crack pattern within the track is
presented in Fig. 1. As the crack curvature was concave with
regard to the sliding direction, cracks occurred ahead of the
tip during scratching. This damage mode is usually called
‘conformal cracking’ [7,8]. Chemical etching of tungsten in
the scratch track showed that cracks propagated through the
interface and within the polyimide substrate. Crack propaga-
tion in the W coating was due to the important strain of the
substrate. Coating and substrate were ploughed by action of
the tangential force applied to the tip. A plastic bow wave
was consequently produced ahead of the tip. On the top of
piled-up region, strain of substrate was important and criti-
cal tensile stress was reached in the coating. Crack propaga-
tion occurred by extension of pre-existing flaws close to the
 J. Ligot et al. / Wear 243 (2000) 85–91
tungsten surface. The cracks were not deflected towards the
interface and they grew into the polyimide substrate. This
behaviour showed the strong adhesion between metal coat-
ing and polymer substrate. Moreover, no delamination or
‘buckling failure’ mode was observed at any of the scratch
modes (ILM, ILM-M, CLM).
3.2. Influence of intrinsic parameters
The influence of the parameters related to testing condi-
tions defined by Steinmann et al. [9] as intrinsic parameters,
was considered in order to improve the interpretation of the
critical loads and to define the suitable parameters for this
type of samples. Coatings were tested in linearly increasing
load modes; scratches were performed at several scratching
speeds of 2, 10, 20 mm min−1 , and under several loading
rates of 3, 10, 30 N min−1 . A minimum of five scratches
was produced under the same conditions to determine the
average value of L1c .
Fig. 2 shows the variation of critical load measured with
different scratching speeds for coatings 0.2 ␮m thick de-
posited at pressures of 0.2, 0.7 and 1.2 Pa. The loading rate
dL/dt was fixed at 10 N min−1 . The critical load decreased
with the increase of the scratching speed. The evolution of
the critical load is shown in Fig. 3 as a function of the load-
ing rate for the same sample. The scratching speed dx/dt
was fixed at 2 mm min−1 . The higher the loading rate, the
higher the critical load became. The origin of this behaviour
is not clear but it could be a consequence of the viscoelastic
response of the polyimide substrate. Vaughn et al. [10] ob-
served indeed the same effect with copper films on PET sub-
strates. These authors have demonstrated that an increase of
the elastic modulus of the polymer with strain rate induces
a decrease of the polymer substrate strain for a given load
[11]. Therefore, if the loading rate dL/dt increases, a higher
load is required to reach the critical strain of the coating and
generate a crack.
Fig. 2. Variation of critical load vs. scratching speed for coatings deposited
at pressures of 0.2, 0.7 and 1.2 Pa. The loading rate dL/dt was fixed at
10 N min−1 in increasing load mode (ILM). Thickness of the coatings
was 200 nm.
87
Fig. 3. Variation of critical load versus loading rate for coatings deposited
at pressures 0.2, 0.7 and 1.2 Pa. The scratching speed dx/dt was fixed at
2 mm min−1 in increasing load mode (ILM). Thickness of the coatings
was 200 nm.
The load gradient can be expressed as (dL/dt)/(dx/dt)=dL/
dx. An increase of Lc with dL/dx was expected from the vari-
ations of critical load described above. The critical load is
plotted in Fig. 4 versus this ratio. The load gradient ranges
from 0.5 up to 15 N mm−1 . The critical load exhibits a sig-
nificant increase which confirms the dependence of Lc on the
intrinsic parameters. It is noteworthy that this dependence
was observed regardless of the extrinsic parameter values,
such as those of deposition argon pressure and tungsten film
thickness.
The development of cracks is linked to pre-existing
defects in the metal coating. The increase in the critical
load with load gradient unit can result from a decrease of
the probability to encounter such defects. This occurs when
the tip moves faster, as proposed by Steinmann et al. [9].
Multipass scratch mode was used to eliminate this statistical
effect.
The differences in the critical load as a function of the de-
position pressure appeared to be more significant at higher
loading rates for a fixed film thickness. It was the reason
Fig. 4. Variation of critical load determined in increasing load mode
(ILM) vs. load gradient for coatings deposited at pressures of 0.2, 0.7
and 1.2 Pa. Thickness of the coatings was 200 nm.
88 J. Ligot et al. / Wear 243 (2000) 85–91
why the highest loading rate was chosen: 30 N min−1 . More-
over, the limits of the apparatus imposed a maximum applied
load of 30 N and therefore a minimum duration of 1 min for
a scratch achieved at a loading rate of 30 N min−1 . Conse-
quently, the scratch length was controlled by the scratching
speed. In order to clearly distinguish the cracks within the
scratch track long scratches were selected for the following
study: 10 mm, with a scratching speed of 10 mm min−1 . The
load gradient was thus fixed at 3 N mm−1 .
3.3. Increasing load mode
Ten passes were performed in the same scratch track for
the wear test (ILM-M) of each sample under linearly in-
creasing load. The critical load was measured by optical
observation after each pass. Fig. 5 illustrates the variation
of critical load with the number of passes. The results ob-
tained at a deposition pressure of 1.2 Pa were representative
of the variations observed at lower pressures. ILM-M tests
disclosed a decrease in the critical load after each pass but
this decrease of Lic became zero after the fifth or sixth pass.
In other words, the additional pass generated a new crack
which corresponded to a load lower than its previous. How-
ever, the critical load levelled off after about six passes. The
next passes did not create any new cracks at a lower load; L10
c
was consequently equal to L6c for the majority of samples.
Fig. 6 combines the critical loads L1c and L10
c , respectively,
determined after the first pass and tenth pass, as a function
of film thickness and deposition pressure. Regardless of film
thickness and deposition pressure, the same trends were ob-
served with the L1c and L10
c values. For a given deposition
pressure the higher the film thickness, the higher were the
critical loads L1c and L10
c . Moreover, Lc and Lc increased
1 10
also with deposition pressure at a fixed thickness. However,
L1c differed from L10
c concerning their dependence on both
film thickness and deposition pressure. For the 200 nm film,
the L1c value for 1.2 Pa was about 20% higher than the value
Fig. 5. Variation of critical load with the number of passes determined
in increasing load multipass mode (ILM-M). Tungsten coatings were
deposited with a deposition pressure of 1.2 Pa and thicknesses of 200,
400 and 600 nm.
Fig. 6. Critical loads, L1c and L10
c , respectively determined after the first
pass and after the tenth pass, as a function of film thickness and deposition
pressure.
obtained for 0.2 Pa, whereas, for the 600 nm thickness, L1c
(1.2 Pa) was about 70% higher than L1c (0.2 Pa). For the thin-
ner films, the critical load L10 c for 1.2 Pa was about 130%
higher than the L10 c value determined for 0.2 Pa, whereas for
the thicker films, L10c (1.2 Pa) was about 25% higher than Lc
10
(0.2 Pa). At the intermediate deposition pressure of 0.7 Pa,
the critical loads L1c and L10 c did not change as described
above. For the 400 nm film thickness, the L1c and L10 c values
were, respectively, similar to the values obtained for 1.2 Pa.
In contrast, for the thicker films, the critical loads of films
deposited at 0.7 Pa were equivalent to the values measured
for films deposited at 0.2 Pa.
With increasing film thickness, the differences of L1c val-
ues with deposition pressure were larger whereas those of
L10
c values were smaller.
The deposition argon pressure especially affects the film
microstructure, the size and density of flaws and also the
internal stresses within the coating [6,12,13]. Such internal
stresses were always compressive for the deposition pres-
sures used [2]. They contribute to the increase of critical load
and the film resistance to crack propagation perpendicular to
the free sample surface. In turn, these compressive stresses
within the coating promote a coating decohesion mechanism
with buckling propagation along the substrate–film interface
[14]. However, as stated earlier no coating delamination was
observed in this study. The internal stresses were almost re-
duced by the cracks created in the track after ten passes.
Hence, the value L10 c being smaller than Lc characterizes
1
the fracture toughness of the coating almost quite free from
internal stresses.
Two observations must be explained: (1) why L1c and L10 c
increased with thickness, and (2) why L1c and L10 c values
were higher for films deposited at higher pressure?
Firstly, the critical load increases with film thickness be-
cause the hardness of the tungsten film increases due to re-
duced influence of the substrate. The load transfer in the
composite film–substrate structure is modified for a harder
coating. The stress gradient along the sample depth induces
a variation of the stress applied to crack surfaces. Although
hardness difference between substrate and film is very high,
 J. Ligot et al. / Wear 243 (2000) 85–91 89

it is generally known that for coatings thinner than 1 ␮m

stresses in the coating are homogeneous and indentation
stresses in the substrate are approximately the same with or
without film, if the load is high enough. This casts doubt
upon the adequacy of this explanation for coatings as thin
as 0.6 ␮m.
In contrast, variation of critical load with coating thick-
ness is linked to the load increase necessary to propagate
the crack for a distance equal to the thickness variation. In-
deed, the cracks observed after scratching were those which
reached the film–substrate interface. Consequently, the de-
pendence of the critical load on film thickness (i.e. length of
observed cracks) can be established, since the pre-existing
cracks grow progressively. Therefore, it must be proved that Fig. 7. Number of cracks generated in constant load mode (CLM) within
fracture toughness of tungsten, hence conditions of fast frac- a scratch track 5 mm long as a function of applied load. Coatings were
ture mode, were never achieved with the loading condi- deposited at 1.2 Pa and with thicknesses of 200, 400 and 600 nm. The
tions of this study. Fracture toughness of tungsten is esti- curves corresponds to the Weibull statistic functions calculated with the
mated to be close to KIC =10 MPa m0.5 [15]. The pre-existing parameters m and La reported in Table 1.
cracks cannot be longer than the larger film thickness of
0.6 ␮m. The tensile stress responsible for crack propagation
should be equal to Meyer’s hardness [16], HM , by analogy increased [5]. Nevertheless, beyond a certain load the num-
with the expression that applies for Hertzian contacts [17]. ber of cracks reached a saturation level, Ns . This constant
HM =L/(␲a2 ), where L is the applied load and a the radius of load has been called the saturation load, Ls . All the data are
contact area. Accordingly, the tensile stress can be estimated presented in Table 1. λs (e, P), for a film thickness e and a
from the expression of the stress intensity factor as KIC =HM deposition pressure P, is the ratio 5 mm/Ns hence the aver-
(␲e)0.5 where e is the film thickness. In this work, L1c , L10
c age spacing between two cracks. Regardless of deposition
or Ls is lower than 10 N and consequently HM ∼7.3 GPa and pressure, the larger the film thickness, the greater was Ls
a∼21 ␮m. Based on width measurements of the residual for the same reason describe section C about Lc variation
scratch track for the critical load, a was always higher. As a with film thickness. However, the λs values did not follow
result, tensile stress was always lower than 7.3 GPa within the same evolution of Ls , as shown in Table 1. For films
the studied load range and the fracture toughness of tungsten of 400 and 600 nm thick and for a given deposition pres-
was never reached. Therefore the pre-existing cracks grew sure, the amounts of cracking were the same (λs (400 nm,
progressively through the metal coating, while the applied P)∼λs (600 nm, P)). As it was shown in ILM-M with L10 c ,
load increased. The thicker the film, the longer the cracking for L≥Ls all flaws being likely to grow in observable cracks
distance through the coating which was necessary for the produced these cracks. Accordingly λs (e, P) allowed to eval-
crack to be observable, was. Consequently the critical load uate the amount of flaws in the film. Therefore λs being
increased with the film thickness. the same for films 400 and 600 nm thick, the flaw volumic
Scratches under constant load were produced and the re- density decreased and the microstructure homogeneity was
sults were subjected to Weibull analysis, as for bulk ceram- enhanced as thickness increased. This trend was especially
ics, in order to obtain information about the flaw size distri-
bution in the tungsten coatings.
Table 1
3.4. Constant load mode Results of the CLM testa
e (nm) λs (␮m) Ls (N) La (N) m
In the second part of the study, tungsten films have been
0.2 Pa 200 37 6.5 4.3 3.4
evaluated by scratching under constant load. The amount of 400 62 7.5 5.4 3.1
cracking, which occurred within the scratch track, was deter- 600 64 10.5 8.1 4.6
mined by optical microscopy. Scratches were independently
0.7 Pa 200 – – – –
achieved for each sample, with different loads increasing 400 62 7.5 6.1 3.4
with increments of 0.5 N. 600 58 9.0 7.3 6.0
Fig. 7 shows the number of cracks generated within a 1.2 Pa 200 28 6.5 4.3 4.3
scratch track 5 mm long, as a function of applied load. This 400 56 7.5 5.7 8.7
behaviour obtained at the higher deposition pressure (1.2 Pa) 600 57 10.0 8.2 5.2
was also representative of those recorded for 0.2 and 0.7 Pa. a λ is the average length between two cracks within the scratch track
s
The characterization in constant load mode disclosed an in- when saturation is reached. Ls is the saturation load. La and m are the
crease of the amount of cracking when the applied load was Weibull parameters.
90 J. Ligot et al. / Wear 243 (2000) 85–91
Fig. 8. Frictional force as a function of applied load in constant load
mode (CLM) for a 600 nm thick film and for deposition pressures of 0.2,
0.7 and 1.2 Pa.
confirmed for film as thinner as 200 nm for which λs (200 nm,
P)<λs (400 nm, P).
The average frictional force, Ft , was measured during
each scratch test and results are shown in Figs. 8 and 9. It
appeared to be practically independent of deposition pres-
sure and film thickness.
The results were analysed by Weibull statistics as defined
by Bull and Rickerby [14]. The cumulative failure probabil-
ity, P(L), was deduced from the expression
 m 
[N (L)] F ing indentation. L1c varies with the intrinsic parameters of
P (L) = = 1 − exp
Ns La
in which N(L) is the number of failures under the load L and
La is a constant equal to the load for which there is a 63.2%
cumulative failure probability. La and m were determined for
each deposition condition and the results are presented in
Table 1. As is shown in Fig. 7 the Weibull statistic function
matches well the experimental results. In the range of thick-
nesses studied, La increased with thickness independently
Fig. 9. Frictional force as a function of applied load in constant load
mode (CLM) for 0.2 Pa deposition pressure and for film thicknesses of
200, 400 and 600 nm.
of deposition pressure, as it was observed for Ls . This ob-
servation confirms that film toughness is not reached when
Ls ≥L and that Ls depends on the crack length.
In fracture mechanics, m is linked to the distribution of
pre-existing crack size. It is difficult to find a monotonous
behaviour between m and the film thickness, and also bet-
ween m and the deposition pressure.
We can suggest the possible changes in the film struc-
ture and microstructure as well as the variations of the pre-
existing crack size distribution and of the conditions for
crack propagation, when both the thickness and deposition
pressure increase. Indeed, for the highest argon deposition
pressures, the films consisted of two crystallographic tung-
sten phases (W␣ and W␤ ) and the ratio W␣ /W␤ changed
with thickness [6,18].
4. Summary
Scratches produced with the Rockwell C indenter of a
microscratch tester on tungsten coatings deposited on poly-
imide substrate create transverse cracks but no film delami-
nation, an indication of the strong adhesion between coating
and substrate. Three scratching modes (ILM, ILM-M and
CLM) were used to determine different critical loads and to
have access to complementary informations. L1c , in increas-
ing load mode (ILM) is a load that characterizes the global
resistance of the metal coating to the cracking under slid-
scratching. L10
c , in multipass increasing load mode (ILM-M)
is a load independent of the internal stresses within the coat-
ing and also of the pre-existing crack size. This value is
useful for engineering calculations, because it estimates the
load below which no crack can be observed. Scratching un-
der constant load mode (CLM) and analysis of cracking by
the Weibull method allow the determination of the statistic
of distribution of pre-existing crack size that could be linked
to coating microstructure. Regardless of thickness tungsten
films sputter-deposited at the highest argon pressure (1.2 Pa)
exhibited the highest fracture toughness.
Acknowledgements
The authors would like to thank P. Leroux and S. Le
Pourhiet for their collaboration and P. Ballester for his help
in manuscript writing.
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