Surface and Coatings Technology 180 181 (2004) 570574

Mechanical properties of nanocomposite and multilayered CrSiN

sputtered thin films
a,*, A. Karimia, J. Esteveb, F. Levy
a
E. Martineza, R. Sanjines
a
Institute of Physics of Complex Matter, FSB-EPFL, CH-1015 Lausanne, Switzerland
`

Departament de Fsica
Aplicada i Optica,
Universitat de Barcelona, Avda. Diagonal 647, 08028 Barcelona, Catalunya, Spain

Abstract
We have investigated the structural and mechanical properties of polycrystalline CrSiN thin films of different morphologies.
The films were deposited by reactive magnetron sputtering at 510 K using two confocal targets of Cr and Si. The structure and
mechanical properties of co-deposited CrSiN films depend on their silicon content. Films with silicon content lower than 3
at.% are fcc Cr1yxSixN compounds with a maximum hardness of 22 GPa. On the contrary, films containing more than 3 at.% of
silicon show the segregation of a SiNx amorphous phase and highly columnar morphology. These samples have low hardness
values (14 GPa). The alternating deposition of CrN and a-SiNx layers disrupts this columnar structure and leads to nanocomposite
films. The hardness of these films varies when the multilayer period is changed, i.e. the CrN crystallite size. A maximum hardness
value (26 GPa) has been found for a nanocomposite structure composed of 4 nm CrN crystallites embedded in amorphous SiNx.
2003 Elsevier B.V. All rights reserved.
Keywords: Nitrides; Silicon nitride; Nanostructures; Multilayers; Hardness

1. Introduction
Recent studies have claimed the superior performance
of CrN films as protective coatings at elevated temperatures due to its excellent oxidation resistance w1x.
However, the main drawback for the use of CrN is still
its hardness (18 GPa) w2x, which even if it is relatively
high, is not good enough to compete with that of TiN
(2123 GPa) w3x. One alternative for improving the
hardness values, keeping at the same time the CrN
oxidation resistance properties, is the formation of nanocrystalline composite materials, following the design
concept proposed by Veprek et al. w4x. These materials
consist of small crystallites (f3 nm size) embedded in
a thin amorphous matrix (f1 nm thickness). The
hardening effect is based on inhibiting the grain boundary sliding by the presence of an amorphous phase,
which will form strong bonds at grain boundaries w5x.
Veprek claimed to deposit superhard nanocomposite
materials with hardness values equal or higher than 40
GPa.
*Corresponding author. LPCM-IPMC, EPFL, CH-1015 Lausanne,
Switzerland. Tel.: q41-21-693-4442; fax: q41-21-693-4666.

E-mail address: rosendo.sanjines@epfl.ch (R. Sanjines).

The superhardening effect has been experimentally

verified in the case of TiSiN (nc-TiNya-Si3 N4 )
w4,6,7x, TiAlSiN (nc-TiAlNya-Si3 N4 ) w8x and
WSiN (nc-W2Nya-Si3N4 ) compounds w4,9,10x. On
the contrary, Nose et al. did not find any superhardening
effect for the ZrSiN system w11x. Therefore, the
factors leading to superhardness and the features
required by the candidate systems are not yet clearly
established. One of these candidate systems is CrSiN,
composed by CrN nanocrystallites and an amorphous
matrix of SiNx. To our knowledge, only a paper concerning CrNySi3N4 nanostructured multilayers has been
published w12x. The authors did not find any superhardening, as hardness values were between those corresponding to CrN and Si3N4.
The aim of this paper is the study of the mechanical
properties of CrSiN thin films. With this purpose, we
have changed the deposition conditions to obtain
Cr1yxSixN ternary phases as well as multilayered CrNy
a-SiNx structures of different morphologies.
2. Experimental
CrSiN thin films were prepared by reactive magnetron sputtering in an AryN2 gas mixture. The deposi-

0257-8972/04/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2003.10.121

E. Martinez et al. / Surface and Coatings Technology 180 181 (2004) 570574

tion system is equipped with two confocal targets of

pure chromium and silicon, 5 cm in diameter. Details
about the deposition system have been reported in Ref.
w13x. The substrates were (1 0 0) silicon wafers, (1 0 0)
double-side polished silicon wafers and thermally oxidized silicon wafers. They were fixed at an intermediate
position between the two targets and they were electrically grounded. The base pressure was lower than
10y5 Pa and the total deposition pressure was 0.45 Pa.
The nitrogen partial pressure was settled at 0.23 Pa
(51% of total pressure) to assure the deposition of the
cubic CrN phase w13x. Substrates were heated to 510 K.
Two different experiments were performed. One is the
deposition of CrSiN films by the co-deposition of Cr
and Si in the reactive sputtering gas. The silicon content
in the films was varied by changing the r.f. power
applied to the Si target from 10 to 160 W, while
maintaining the Cr target d.c. power constant at 175 W
w13x. The other experiment is the alternating deposition
of Cr and Si in the presence of the reactive sputtering
gas to form multilayered CrNya-SiNx structures. In this
case, the power applied to the Cr and the Si targets was
fixed at 175 and 160 W, respectively. Opening and
closing the shutters, while maintaining both plasmas
always lighted, achieved the multilayered structure.
Film thickness was measured with a surface profiler
(TENCOR Alpha-Step 500). Film composition was
determined by electron probe microanalysis with a
CAMECA SX 50 apparatus at 8 kV of acceleration
voltage. The microstructure was investigated by X-ray
diffraction in grazing incidence (as58) and u2u configurations (Cu Ka radiation). Scanning electron
microscopy (SEM) was used to study the film morphology using a Philips XL30 FEG microscope. Crosssection transmission electron microscopy (TEM) images
were obtained with a 200 kV JEOL JEM-2010F and a
Hitachi HF-2000 microscope, both equipped with EELS
facilities. Optical signatures of silicon nitride vibrational
modes were obtained by Fourier transform infrared
spectroscopy (FTIR) in the transmission mode from 400
to 1200 cmy1. Mechanical properties were evaluated by
nanoindentation (Nano IndenterXP, Nano Instruments).
Nanoindentation measurements were performed with a
Berkovich indenter using the continuous stiffness measurement technique w14x.
3. Results
3.1. Co-deposited CrSiN films
Films with silicon content up to 3 at.% are fcc
Cr1yxSixN phases. For Si content higher than 3 at.%,
the silicon segregates at the grain boundaries to form an
a-SiNx phase. In addition, the film morphology changes
from columnar-triangular shape to columnar-needle
shape (1 1 1) oriented. The mechanical properties are

571

Fig. 1. XRD patterns measured in grazing incidence configuration

(as58) for CrNya-SiNx multilayers of different CrN layer thicknesses, lCrN.

connected with the structural and morphological changes

observed in the CrSiN films as the silicon content is
increased. Accordingly, hardness increases from 18 GPa
(CrN) to 22 GPa (CrSiN with 3 at.% silicon) and
then decreases to 14 GPa (CrSiN with 7 at.% silicon)
w13x.
3.2. CrNya-SiNx alternating deposition films
The objective of the alternating deposition process
was to disrupt the columnar growth of the CrN and to
avoid the presence of large CrN crystallites. As a first
attempt, a set of CrNya-SiNx multilayers was deposited
by fixing the a-SiNx layer thickness at 2 nm, while the
CrN layer thickness was varied between 60 and 2 nm.
As the thickness of the CrN layer is decreased, the
crystallite size decreases, as it can be measured from
the broadening of the diffraction peaks (Fig. 1). For
films with CrN layer thickness of 11 nm or below
(measured from the deposition rate), the layer thickness
coincides with the crystallite size (measured from XRD
and TEM techniques). The presence of the SiNx phase
was noticed from infrared spectroscopy measurements.
The absorption spectra exhibit a broad absorption band
centered at 840 cmy1 (Fig. 2). The deconvolution of
this band, given three Gaussian peaks centered at 800,
840 and 970 cmy1, attributed to vibrational modes of
SiNx w15x. SEM pictures showed a multilayered structure
with the amorphous layer disrupting the typical columnar growth found for the co-deposited CrSiN samples

572

E. Martinez et al. / Surface and Coatings Technology 180 181 (2004) 570574

Fig. 4. TEM images corresponding to a CrNya-SiNx multilayer with

a CrN layer thickness ls10 nm. (a) Bright-field image; (b) darkfield image showing the interpenetration of the a-SiNx layer between
the CrN crystallites.

Fig. 2. FTIR absorbance spectra measured for CrNya-SiNx multilayers

of different CrN layer thicknesses, lCrN.

(Fig. 3). TEM measurements showed a structure composed by regular-cubic CrN nanocrystallites separated
by a-SiNx layers (Fig. 4a). It is worth noticing that the
interface between the CrN and the a-SiNx layers is not
abrupt. The amorphous phase diffuses between the CrN
grains (Fig. 4b), forming a nanocomposite structure of
CrN crystallites embedded in the a-SiNx phase. Hardness
increases up to a maximum of 25 GPa when decreasing
the crystallite size, and then decreases for CrN crystallite
sizes lower than 4 nm (Fig. 5).
A second set of CrNya-SiNx multilayers was deposited with increased hardness. The CrN layer thickness
was fixed at 4 nm while the a-SiNx layer thickness was

Fig. 3. SEM images corresponding to: (a) co-deposited CrSiN film

(7 at.% of silicon) (1 1 1) oriented; (b) CrNya-SiNx multilayer with
a CrN layer thickness lCrNs35 nm.

varied from 2 to 0.2 nm. This process can lead to an

optimum CrNya-SiNx nanostructure for which the percentage of the amorphous phase in contact with the
small CrN crystallites is maximized. XRD measurements
showed that for a-SiNx layers of nominal thickness
below 1 nm, the CrN crystallite size increases (Fig. 6)
and the structure becomes again highly columnar. The
hardness showed a maximum value of 26 GPa for the
sample with 1.2-nm-thick a-SiNx layer (22 vol.%) (Fig.
7).

Fig. 5. Hardness of CrNya-SiNx multilayers as a function of the CrN

crystallite size. The dashed line indicates the rule of mixtures hardness
values obtained according the equation H(Aa, Bb)swaH(A)q
bH(B)xy(aqb) where a and b are the volume fraction of CrN and aSiNx (calculated from lCrN and lSiNx). The hardness of a pure
a-SiNx film was measured as 26 GPa.

E. Martinez et al. / Surface and Coatings Technology 180 181 (2004) 570574

Fig. 6. XRD patterns measured in grazing incidence configuration

(as58) for CrNya-SiNx multilayers of a fixed CrN layer thickness
lCrNs4 nm and different a-SiNx layer thickness.

4. Discussion
The co-deposited films with CrNya-SiNx structure did
not show any hardness improvement, but a decrease in
hardness values (14 GPa). This decrease can be related
to its highly columnar morphology with large crystallites
()100 nm) not strongly bonded. The a-SiNx amorphous
phase between columns is not strong enough to stop the
microcrack growth. This can be attributed to the low
strength of the interface between CrN and a-SiNx at the
grain boundaries andyor at the presence of voids
between the two phases. In contrast, the CrNya-SiNx
multilayered nanocomposite films exhibit hardness values that significantly exceed that of expected from the
rule of mixtures (Fig. 5), evidencing the importance of
the structure and morphology. The different hardness
behavior found as a function of the CrN crystallite size
can be explained as follows. For large CrN crystallites
between 12 and 22 nm in size (region (a) in Fig. 5),
the increasing of hardness values H while decreasing
the crystallite size d follows a similar dependence than
that stated by the HallPetch relationship (Had y0.5)
w16,17x. In fact, it seems that this relationship could be
extended down to a crystallite sizes below 50 nm w4,18x
even if it is considered as a semiempirical relationship.
The hardening effect is attributed to several mechanisms
that can contribute in a complicated way, as grain
boundary hardening and the ability to withstand the
growth of microcracks. For crystallite size less than 10
nm, the grain boundary sliding mechanisms become

573

important w5x and a deviation from the HallPetch

relationship is expected, as observed in Fig. 5. However,
for CrN crystallites between 9 and 4 nm in size (region
(b) in Fig. 5), the hardness increases up to 25 GPa. In
this region, crystallites are small enough to avoid dislocation generation and motion w5x and the microcracks
propagation is hindered by the presence of the thin
amorphous layer imbedding the crystallites. These
results are similar to those reported by Patscheider et al.
for TiNya-Si3N4 films w19x. However, in contrast with
the results obtained for TiNya-Si3 N4 , the CrNya-SiNx
system does not exhibit a superhardness effect. This
could be related to the fact that the CrN electronic
configuration suggests a less covalent bonding between
CrN and a-SiNx than in the case of TiN and a-Si3N4.
When the crystallite size decreases down to 4 nm the
hardness decreases again (region (c) in Fig. 5). In this
case, the amount of amorphous material among the
crystals is too large to maintain strong bonds between
the two phases.
When decreasing the thickness of the a-SiNx layer
while maintaining the CrN crystallite size at 4 nm, we
also observe significant changes in hardness values. A
maximum hardness of 26 GPa is observed when the
layer thickness of the amorphous phase is approximately
1 nm (Fig. 7). This thickness value corresponds to that
observed for the SiNx amorphous phase in superhard
TiNya-Si3N4 nanocomposites reported by Veprek et al.
w4,5x. This situation corresponds to that in which both
phases can have a full interpenetration, i.e. the percolation threshold w4,19x. However, when decreasing aSiNx layer thickness, the amount of the amorphous

Fig. 7. Hardness of CrNya-SiNx multilayers (CrN layer thickness of

lCrNs4 nm) as a function of the a-SiNx layer thickness.

574

E. Martinez et al. / Surface and Coatings Technology 180 181 (2004) 570574

phase is not enough to coat entirely the CrN grains and

to avoid the columnar growth, as it was the case for the
co-deposited CrNya-SiNx films with Si content less than
3 at.%.

mann from the Centre Interdisciplinaire de Microscopie

Electronique (CIME) of the EPFL and Dr Jordi Arbiol
from the SCT of the University of Barcelona are
gratefully acknowledged for the TEM measurements.

5. Conclusion

References

Nanocomposite CrNya-SiNx thin films can be deposited by reactive magnetron sputtering from the codeposition of Cr and Si targets in the presence of the
reactive gas mixture and from the alternating deposition
of CrN and a-SiNx as multilayered structures. Codeposited CrNya-SiNx films are relatively soft (14 GPa),
while nanocomposite multilayered structures exhibit a
maximum hardness value of 26 GPa, much higher than
that of pure CrN film (18 GPa). Morphological and
structural changes are found to be responsible for the
difference in hardness values. Co-deposited CrNyaSiNx films have a highly columnar structure with large
crystallites and a thin a-SiNx layer between columns.
The interface between two phases is not strong enough
to bond them and the structure is soft and prone to
microcrack propagation. In the case of CrNya-SiNx
multilayered films, the presence of a thin amorphous
layer (thickness f1 nm) as well as the small CrN
crystallite size (f4 nm) results in high hardness values.
This particular microstructure hinders the multiplication
and propagation of dislocations and the growth of
microcracks.
Acknowledgments
The authors are grateful to the Swiss National
Research Foundation for financial support. Prof. Stadel-

w1x P. Hones, C. Zakri, P.E. Schmid, F. Levy,

O.R. Shojaei, Appl.

Phys. Lett. 76 (22) (2000) 3194.
w2x S.J. Bull, D.S. Rickerby, Surf. Coat. Technol. 4344 (1990)
732.
w3x P. Yashar, S.A. Barnett, J. Rechner, W.D. Sproul, J. Vac. Sci.
Technol. A 16 (1998) 2913.
w4x S. Veprek, M. Haussmann, S. Reiprich, J. Vac. Sci. Technol.
A 14 (1996) 46.
w5x S. Veprek, J. Vac. Sci. Technol. A 17 (1999) 2401.
w6x M. Diserens, J. Patscheider, F. Levy,

Surf. Coat. Technol.

120121 (1999) 158.
w7x H.D. Ma nnling, D.S. Patil, K. Moto, M. Jilek, S. Veprek,
Surf. Coat. Technol. 146147 (2001) 263.
w8x E. Ribeiro, A. Malczyk, S. Carvalho, et al., Surf. Coat. Technol.
151152 (2002) 515.
w9x C. Louro, A. Cavaleiro, Surf. Coat. Technol. 116119 (1999)
74.
w10x A. Cavaleiro, C. Louro, Vacuum 64 (2002) 211.
w11x M. Nose, W.A. Chiou, M. Zhou, T. Mae, M. Meshii, J. Vac.
Sci. Technol. A 20 (2002) 823.
w12x J. Xu, K. Hattori, Y. Seino, I. Kojima, Thin Solid Films 414
(2002) 239.
w13x E. Martinez, R. Sanjines, O. Banakh, F. Levy,

Thin Solid
Films, in press.
w14x W.C. Oliver, G.M. Pharr, J. Mater. Res. 7 (1992) 1564.
w15x Y.C. Liu, K. Furukawa, D.W. Gao, H. Nakashima, K. Uchino,
K. Muraoka, Appl. Surf. Sci. 121122 (1997) 233.
w16x E.O. Hall, Proc. Phys. Soc. Lond. Sect. B 64 (1951) 747.
w17x N.J. Petch, J. Iron Steel Inst. Lond. 174 (1953) 25.
w18x E. Arzt, Acta Mater. 46 (1998) 5611.
w19x J. Patscheider, T. Zehnder, M. Diserens, Surf. Coat. Technol.
146147 (2001) 201.