Materials Science and Engineering A340 (2003) 281
/285

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Measurement of hardness of superhard films by microindentation

J. Musil *, H. Zeman, F. Kunc, J. Vlček
Department of Physics, University of West Bohemia, PO Box 314, 306 14 Plzeň, Czech Republic

Received 3 July 2001; received in revised form 25 October 2001

Abstract

A critical analysis is presented of the measurement by microindentation of the hardness of superhard films with hardness, H,
exceeding 50 GPa. This analysis shows that a very high hardness of the Ti
/Si
/N nanocomposite film reaching a value of 105 GPa,
which was recently reported, is hardly a correct value and so till now, very probably, no material harder than diamond has been
prepared.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Superhard films; Hardness; Measurement by microindentation

1. Introduction requires them to be answered. The main aim of this

Recently, S. Vepřek and his coworkers reported that
ultrahard nanocomposite coatings nc-TiN/a- and nc-
TiSi2, with hardness exceeding 100 GPa, were prepared
by a plasma CVD process [1
/6]. To our knowledge up
to now, no other laboratory in the world has succeeded
in repeating this experiment to prepare the nanocompo-
site films with hardnesses exceeding 100 GPa, i.e. to
prepare a material harder than diamond. Therefore, it is
not surprising that considerable attention is now de-
voted to answering the following questions: (i) Is it
really possible to prepare materials harder than dia-
mond? (ii) Is it possible to measure the hardness of a
material that is harder than diamond by an indentation
technique using a diamond indenter? (iii) Can a meth-
odology of hardness measurement by a microindenta-
tion technique, developed and currently used for the
measurement of hard coatings, be used for the measure-
ment of superhard coatings with the hardness larger
than 50 GPa? In spite of the fact that these questions are
very difficult, further progress in material science
* Corresponding author. Tel.: /420-19-742-3136; fax: /420-19-
742-2825
E-mail address: musil@kfy.zcu.cz (J. Musil).
0921-5093/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 1 - 5 0 9 3 ( 0 2 ) 0 0 1 9 4 - 6
communication is to contribute to the answering of the
third question, which, in our opinion, is the simplest
one.
2. Results and discussion
The mechanical behavior of hard and superhard
coatings is usually characterized by their hardness, H,
effective Young’s modulus, E */E /(1/n2), and elastic
recovery, We. These quantities are evaluated from
loading
/unloading curves measured by microindenta-
tion using a microhardness tester. A correct determina-
tion of H, E *, and We is, however, difficult because the
measured values of these quantities strongly vary with
the diamond indenter load, L , used in their measure-
ments. It is well known that the correct value of H is
that value which does not depend on L , i.e. it is
measured at a load L which lies in the interval where
H (L ) :/constant. At present it is accepted that a
maximum load, Lmax, must meet the following inequal-
ity: (d/h)max 5/0.1; here d is the indenter depth and h is
the film thickness. On the contrary, the smallest loads L
of about 10
/20 mN are currently considered as suffi-
cient to fit the interval L , where H(L ):/constant. The
last statement is, however, justified only for hard films
with hardness H 5/50 GPa.
282 J. Musil et al. / Materials Science and Engineering A340 (2003) 281
/285
Fig. 1. The hardness H of sputtered 2.4 mm thick Ti
/Al
/N film, 6 mm thick Zr
/Cu
/N film and 4 mm thick Ti
/B film and the ratio d /h of the
indentation depth d and the thickness h of 4 mm thick Ti
/B film as a function of the diamond indenter load L .
Recent experiments [7] show that for superhard (/50
GPa) films the region H (L ) :/constant shifts to higher
values of L , with increasing values of the elastic
recovery, We, of the film (see Fig. 1). This is due to
the fact that a gradient dH/dL strongly decreases with
increasing H above 50 GPa. The shift of the region,
where H (L ):/constant, to higher values of L is greater
the greater is the film hardness H . This means that the
correct value of the hardness, Hcorrect, of superhard films
can be measured only at higher loads L , which already
lie in the interval of L , where H(L ):/constant. The
minimum load, Lmin, which gives Hcorrect increases with
increasing H and for the film with H :/70 GPa achieves
already more than 50 mN (see Fig. 1). This experiment
clearly shows that the hardness measured at L B/Lmin is
higher than a correct value of Hcorrect of the film, i.e.
Hmeas. /Hcorrect.
To determine the correct value of Hcorrect for harder
(/70 GPa) films, still higher values of Lmin must be
used. It means that a very high hardness of the nc-TiN/
a-Si3N4 nanocomposite film, reaching a value of 105
GPa, reported by Vepřek [1] and measured at 50 mN
(figure 4 in [1]), is hardly a correct value. This conclu-
sion is supported also by his recent measurements of the
load-independent Vickers hardness of multiphase nc-
TiN/a-Si3N4/a- and nc-TiSi2 nanocomposite films versus
the total Si content (figure 5 in [6]), which show that a
maximum hardness, with the exception of only one film
containing 20 at.% Si, achieves about 80
/85 GPa. This
hardness seems to be a reasonable value. This fact,
however, means that till now no material harder than
diamond has been prepared and the demonstration of
the possibility to produce such materials remains an
open problem.
The increase in the film hardness H is always
accompanied by an increase of the elastic recovery We,
see for instance [8], where general relationships between
H , We, and E * are given for different films. There are,
however, films with a low (5/40 GPa) hardness which
also exhibit high values of We. Therefore, it is still
necessary to explain how the elastic recovery We
influences a course of the dependence H(L ). Such
experiments were carried out for 4 mm thick Ti
/B film
with high H and high We and 5 mm thick Al
/Si
/Cu
/N
film with low H and high We. The obtained results are
given in Fig. 2. From this figure it is seen that the high
value of We alone is not sufficient to decrease the
gradient dH/dL at low indenter loads, see the depen-
dence H /f (L ) for Al
/Si
/Cu
/N film.This means that
films with low ( 5/40 GPa) hardness and high ( ]/70%)
elastic recovery can be correctly measured at low loads
L of about 20 mN. To decrease the gradient dH/dL a
combined action of both high H and high We is
necessary. Just this is the case of superhard films.
Also, it is worthwhile to note that the dependence
We /f (L ) does not exhibit a plateau in some interval
L but gradually decreases with increasing L . Therefore,
the elastic recovery We always depends on L and is the
lower, the higher is the indenter load L used in
measurement.
The hardness H of the film is determined from a
plastic component of the film deformation induced by
the diamond indenter during its penetration into a
surface of the film. Therefore, the measured quantity
 J. Musil et al. / Materials Science and Engineering A340 (2003) 281
/285 283

Fig. 2. (a) Hardness H and (b) the elastic recovery We of 5 mm thick Al
/Si
/Cu
/N and 4 mm thick Ti
/B film as a function of the diamond indenter
load L .

is also called as a plastic hardness. The accuracy of the
hardness measurement, however, decreases for high (]/
60 GPa) hardnesses because the elastic recovery We of
the film achieves very high values of 70
/90% and due to
this fact the plastic component of deformation strongly
decreases (the area between the loading and unloading
curves is very small and represents only 30
/10% of the
total deformation energy). Therefore, some investigators
suggest to use an universal hardness HU for the
characterization of superhard films, which is based on
both plastic and elastic component of the film deforma-
tion. The universal hardness HU, however, also exhibits
specific features and so this quantity has to be used
correctly. The main features of HU are the following:
a) The universal hardness HU first increases with
increasing H but from a critical value of hardness
Hc the HU practically does not change with
increasing H /Hc, see Fig. 3(a). This is a direct
consequence of a correction procedure used in
evaluation of HU at low values of L .
b) The universal hardness HU depends not only on the
hardness H but also on the elastic recovery We of
the film, see Fig. 3(a and b). The HU first increases
284 J. Musil et al. / Materials Science and Engineering A340 (2003) 281
/285

Fig. 3. The dependence of the universal hardness (a) HU/f (H ) and (b) HU/f (We) for Ti
/B and Al
/Si
/Cu
/N [9] films magnetron sputtered
from TiB2 target and composed Al
/Si
/Cu (Al-10at.%Si target with a Cu fixing ring) target, respectively.

with increasing We but for We ]/75% the HU either
saturates at a value of about 20 GPa (superhard Ti
/
B film) or strongly oscillates around a value of
about 11.5 GPa (hard Al
/Si
/Cu
/N film). This
experiment shows that (i) HU cannot be used to
characterize hard films exhibiting a high elastic
recovery We ]/75%, (ii) high values of We ]/75%
can be measured not only for superhard (/40 GPa)
films but also for hard (B/40 GPa) films and (iii)
films with a high elastic recovery We ]/75% can
exhibit very different values of HU which strongly
depend on their hardness H and effective Young’s
modulus E *. This experiment clearly shows that the
universal hardness HU is not a good quantity which
can be used to characterize the hardness of super-
hard films.
3. Conclusions
In summary, the correct value of the hardness of
superhard (/60 GPa) films has to be measured at
higher ( /50 mN) loads L because only in this interval
of the indenter loads L the film hardness H(L ):/
constant. The minimum load Lmin, which gives a correct
hardness of measured superhard film is the higher the
 J. Musil et al. / Materials Science and Engineering A340 (2003) 281
/285
higher is the film hardness H. It is due to the fact that
the gradient dH/dL decreases at low values of L with
both high H and high We and the region where H(L ):/
constant shifts to higher values of L .
Acknowledgements
This work was supported in part by the Ministry of
Education of the Czech Republic under Projects Num-
ber MSM 235200002, ME 173/2001 and ME 203/2001.
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