Tribology International 82 (2015) 8994

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Tribology International
journal homepage: www.elsevier.com/locate/triboint

Tribological characterization of chemical vapor deposited

Co and Co3O4 thin lms for sensing reliability
in engineering applications
Elias P. Koumoulos a, Vassileios Markakis a, Vasiliki P. Tsikourkitoudi a,
Costas A. Charitidis a,n, Nikolaos Papadopoulos b, Evangelos Hristoforou b
a
b

School of Chemical Engineering, National Technical University of Athens, 9 Heroon Polytechniou Street, Zographos, Athens 15780, Greece
School of Mining Engineering and Metallurgy, National Technical University of Athens, 9 Heroon Polytechniou Street, Zographos, Athens GR-157 80, Greece

art ic l e i nf o

a b s t r a c t

Article history:
Received 7 March 2014
Received in revised form
23 July 2014
Accepted 16 September 2014
Available online 17 October 2014

In the present study, nanoindentation and nanoscratch techniques are applied in order to obtain the
nanomechanical properties (hardness, H, and elastic modulus, E) of chemical vapor deposited Co and Co3O4
thin lms (promising candidates for magnetic sensing and data storage applications) and evaluate the
functionality of the thin lmsubstrate system. A wear analysis is also performed based on the H/E ratio.
& 2014 Elsevier Ltd. All rights reserved.

Keywords:
Cobalt oxide
Thin lms
Nanoindentation
Coefcient of friction

1. Introduction
The mechanical and tribological behavior of magnetic and storage
devices is of critical importance in determining long-term stability and
reliability of such devices. The good maintenance of the mechanical
and tribological properties of the aforementioned devices can signicantly impact their commercialization. Nanoindentation technique
can be a useful tool for the measurement of stresses for the successful
and reliable operation of such devices. The variation of nanomechanical/nanotribological response of sensors should be kept within a
narrow range (dened percentage of range). Nanoscratch testing is a
versatile tool for analysis of the mechanical attributes of thin lms and
bulk materials and can be used for a plethora of tests, where a single
scratch with a ramped load is useful for critical load, lm adhesion and
mar studies [1]. Nanoscratch data, coupled with scanning probe
microscope (SPM) images, provide detailed information concerning a
material's behavior under simultaneous normal and lateral stresses.
In the present study, nanoindentation and nanoscratch techniques are utilized in order to investigate the nanomechanical (i.e.

Corresponding author. Tel.: 30 2107724046; fax: 30 2107723323.

E-mail addresses: elikoum@chemeng.ntua.gr (E.P. Koumoulos),
vmarkakis@chemeng.ntua.gr (V. Markakis),
vasiatsik@yahoo.gr (V.P. Tsikourkitoudi),
charitidis@chemeng.ntua.gr (C.A. Charitidis),
nickpapss@yahoo.gr (N. Papadopoulos), eh@metal.ntua.gr (E. Hristoforou).
http://dx.doi.org/10.1016/j.triboint.2014.09.018
0301-679X/& 2014 Elsevier Ltd. All rights reserved.

hardness, H, and elastic modulus, E) and nanotribological properties

of chemical vapor deposited (CVD) Co and Co3O4 thin lms, which
can be used in innovative sensing and data storage applications due
to their useful properties [2]. Cobalt thin lms appear as a promising
perspective regarding sensors and magnetic devices, since cobalt
exhibits the highest magnetic anisotropy among transition metals
[3]. Co3O4 thin lms have also been considered for uses as magnetic
detectors, counter electrodes, humidity or oxygen optical sensors [4],
solar-selective absorbers and protective layers [2]. CVD is a widely
used technique for the production of highly dense lms with good
adhesion to the substrate [5].

2. Experimental section
The lms were grown in a vertical, cylindrical metallorganic CVD
stainless steel reactor, specically developed for the deposition of
magnetic lms, either singled or multilayered [56]. The reactor had
computer controlled switching of gases for abrupt transients during
deposition of multilayered structures. It also employed two independent precursor lines and four separate gas delivery lines for maintaining inert, (He or Ar), reductive (H2) or oxidizing (O2) atmosphere.
Prior to reactor's entrance heat traced lines were used. The Co lms
were deposited from a cobalt carbonyl precursor onto a SiO2
substrate. The cobalt carbonyl precursor was introduced to the
reactor as an aerosol mixture, formed by the dissolution of cobalt

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carbonyl into dichloromethane, 0.1 M concentrated. In a typical

experiment a liquid (solution) ow of 7 g/h was mixed with a
hydrogen gas ow of 0.05 l/min at 27 1C. The mixture (aerosol) was
then introduced to the reactor, the temperature of which had been
adjusted to 140 1C; further details are reported elsewhere [6].
As far as the deposition of the Co3O4 is concerned, the substrate (Si)
was loaded and the reactor was purged with an argon ow of 0.75 l/h,
while the susceptor was heated to the desired temperature (450 1C).
Then a solid inclusion complex (placed in a specialized glass reservoir)
of -cyclodextrin with CoI2 was sublimed at 115 oC, and the vapors
were introduced into the reactor with the aid of a constant O2 ow of
50 ml/min; further details are reported elsewhere [6]. The thickness of
the produced Co and Co3O4 lms ranged  120150 nm.
X-ray diffraction (XRD) tests were conducted using a Siemens
D5000 diffractometer with nickel-ltered CuK1 radiation
(1.5405 ), at 40 kV and 30 mA.
The nanoindentation and nanotribological tests in this work were
performed using a nanomechanical test instrument equipped with a
Berkovich tip (120 nm tip radius) allowing the application of loads
from 1 to 30,000 N. In all depth-sensing tests, a total of 10 indents
were averaged to determine the mean H and E values for statistical
purposes, with a spacing of 50 m ( 45% relative humidity, 23 1C).
The above instrument is equipped with a scanning probe microscope
(SPM), in which the sharp tip moves in a raster scan pattern across a
sample surface using a three-axis piezo positioner.
The scratch tests performed in this work included three main
segments. Firstly, a pre-scratch scan under a very low load (0.2 N)

was carried out. Then, the indenter scraped the sample under a
ramp loading from an initial load of 0.2 N to a maximum value of
500 N at the end of the scratch. The scratch path was 10 m and
the tip velocity 0.2 m/s. Finally, a post-scratch was carried under
a low load (2 ). he applied load during the initial scratch and
post-scratch was very low in order to avoid any damage or
permanent deformation of the lms. In all scratch tests, a total
of 5 scratches were averaged for statistical purposes, with a
spacing of 10 m (  45% relative humidity, 23 1C).

3. Results and discussion

3.1. X-ray diffraction/scanning electron microscopy
Cobalt oxide thin lm was deposited in the form of Co3O4.
Surprisingly, no phases corresponding to oxides of divalent cobalt
were detected (Fig. 1a). Intermediate phases of cobalt silicides
(Si content 59.67% w/w) were detected, probably due to the
relatively high deposition temperature, which allowed diffusion
of Si out from the substrate. Discrete peaks corresponding to
typical Si angles of diffraction were detected (Fig. 1b), but this was,
to some extent, attributed to the lm's low thickness, which has
been proven by AFM and MFM measurements (presented elsewhere [6]). The presence of peaks corresponding to Si angles can
be attributed to the free from deposition wafer area that is left for
many reasons, one of which is to directly measure the thickness of

Fig. 1. X-ray diffraction of (a) Co3O4 and (b) Co thin lms, respectively.

Fig. 2. Cross section images of (a) Co3O4 and (b) Co thin lms, respectively.

E.P. Koumoulos et al. / Tribology International 82 (2015) 8994

the thin lm. The cross section images of both thin lms were
determined by scanning electron microscopy (SEM) using a
PHILIPS Quanta Inspect (FEI Company) microscope with W (tungsten) lament 25 KV(Fig. 2).

3.2. Loaddisplacement curves

It is important to evaluate the nanomechanical response in the
overall tribological characterization of materials, as the contact
between surfaces is usually initiated by the contact between surface
asperities with contact areas only a few tens of square nanometers.
In the present work, the loadunload curves of the probed materials
are presented in Fig. 3 (comparison for applied loads of 500 and
1000 ). Co3O4 thin lm exhibits higher resistance to applied load
(i.e. higher applied load values are needed in order to reach the
same displacement). In the case of Co, greater plasticity is revealed,
i.e. energy stored at the material after the indentation is over (total
integration of curve area). The nanomechanical properties of the
thin lms, i.e. H and E, are presented elsewhere [7] and are in good
agreement with similar measurements of the literature [89].
Cobalt thin lm exhibit local changes (discontinuities), i.e. changes
in the slope, referred as pop-ins and elbows in the loading and in
the unloading curve, respectively [7]. During the pop-in, the
indenter tip penetrates in the sample without an increase in the
applied load. The rst pop-in in each sample reveals the onset of

500

Co3O4

Load (N)

400

H = 11 GPa
E = 64 GPa

300

Co
H = 5 GPa
E = 64 GPa

200

100

0
0

10

20

30

40

50

60

70

Displacement (nm)
Fig. 3. Loadunload curves of Co (black) and Co3O4 (red) thin lms (applied load of
500 ) (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this article.).

91

plasticity, i.e. the rst point at which plastic yield occurs. The onset
of plasticity occurs at  10 nm for each thin lm. In this stage, the
nanoindenter can be approximated as spherical and the experimental data deviate from the fully elastic curve. For lower loads
than the load where the onset of plasticity occurs, reversibility of
the indentations performed is observed. The pop-ins indicate a
redistribution of material around the indentation site [7].
In Fig. 4, SPM images of Co and Co3O4 thin lms are presented
for applied loads of 2500 and 5000 ; the indents are noted in
black circle.
3.3. Wear analysis
The H/E ratio is of signicant interest in tribology, as it can be
used as a ranking parameter for materials in terms of wear. This
ratio multiplied by a geometric factor is the plasticity index,
which is a valuable measure for the determination of the limit of
elastic behavior in a surface contact (describes the deformation
properties of rough surfaces) [10]. Fig. 5 shows the H/E ratio as a
function of the displacement of the indenter. The Co3O4 thin lm
exhibits higher resistance to wear in comparison to the Co
thin lm.
A high H/En value means a reduced contact pressure, because
the applied load is distributed over a larger area. A high H/E ratio is
related to a high elastic strain prior to the plastic deformation,
while it has long been known that, in a tribo-contact event
between rough surfaces, purely elastic contact is desired for wear
reduction [7].
Adhesion relation of a coating with a substrate is conrmed by
using the Tresca's yield criterion and Tabor's relation, according to
which, the load at the onset of yielding is proportional to H3/E2. The
term H3/E2 combines H and E values of a material and describes the
amount of elasticity exhibited by the lm. In particular, high (low)
values of H3/E2 indicate a highly elastic (plastic) behavior of the lm
under contact events (Fig. 6) [10,11]. The transition of lm behavior
due to the interface is evidenced, in a slightly lower displacement
when compared with total lm thickness (o150 nm).
It is known that many of the mechanisms of lm failure begin
with or directly involve plastic deformation. Consequently, a
particular concern in the usefulness of thin lms as protective
overcoat materials in hard disk and/or wear-resistant applications
is that these lms must be highly resistant to plastic deformation
during contact events. The lm has to undergo a high proportion
of elastic deformation occurring when indenting, resulting in high
values of H (which reect the small amounts of plastic deformation occurring) (Figs. 3, 5); cobalt oxide thin lm exhibit such
behavior.

Fig. 4. 3D SPM image of indents (2500 and 5000 N) on (a) Co and (b) Co3O4 thin lm (image size 10  10 m2).

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E.P. Koumoulos et al. / Tribology International 82 (2015) 8994

0.35

0.5

film
thickness

0.30

Co3O4

Co

0.4

Coefficient of Friction

0.25

H/E

0.20
0.15
0.10

0.3

0.2

Co3O4
0.1

0.05

Co
0.00
0

100

200

300

400

500

0.0

600

-4

Displacement (nm)

H /E

film
thickness

100

Co thin film
Co3O4 thin film

200

300

Scratch path (nm)

Fig. 5. Hardness to modulus ratio (resistance to wear) as a function of the

displacement of the indenter for both thin lms.

0.90
0.85
0.80
0.75
0.70
0.65
0.60
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00

-2

400

500

Displacement (nm)
Fig. 6. H3/E2 as a function of the displacement of the indenter for both thin lms.

3.4. Nanoscratch analysis

In Fig. 7, the coefcient of friction of the two thin lms is
presented in accordance to the scratch path. The coefcient of
friction is the ratio of the lateral forces to the normal forces and
can be expressed as the sum of adhesive and plowing friction
coefcient. The Co3O4 thin lm exhibits lower coefcient of
friction compared to the Co thin lm (low wear, in line with H/E
and H3/E2).
In Fig. 8, nanoscratch depth proles are presented for maximum normal load of 500 . The scratch scan curve corresponds
to tip penetration prole during testing and the post-scratch curve
corresponds to the nal prole of the surface after scratching (i.e.
plastic deformation of the probed lm). The difference between
scratch and post-scratch curve determines the elastic recovery of
the lms. The statistical error for the scratch depths is less than
10 nm, while the displacement resolution of the nano-indenter
used in this work is better than 0.04 nm, making it possible to
compare the scratch depths of different lms. As it can be
observed in Fig. 7, the deformation of the lms is mainly plastic
all over the scratch path. As far as the Co thin lm is concerned,
uctuations during scratch can be observed indicating possible
failure of the lm. The increase in displacement during postscratch can be attributed to a late recovery of deformation of the

Fig. 7. Coefcient of friction for both thin lms.

thin lm in comparison to the substrate, a fact that induces shear

stresses along the interface causing spallation of the lm [1112].
No sharp deviation is observed in the scratch curve of the Co3O4
thin lm. Thus, the lm has not been peeled off during load
scratch process. However, a low increase in the deformation
displacement can be observed, indicating a critical load
(LcL 150 ) for the delamination of the lm, caused by high
compressive stresses. The load values, corresponding to the point
where the Co3O4 thin lm fails during post-scratch, are almost
equal to 150 and 290 N. The absence of uctuations in the post
scan curve for a scratch depth larger than 20 nm implies that the
lm does not delaminate after unloading, showing good adhesion
to the substrate despite the relative high stress values and there is
no cracks generation, material removal and debris. These events
show that during scratching, plastic deformation successively
occurs with increasing normal load due to the high elastic
deformation, and lm does not delaminate up to the normal load
of 290 mN. In Fig. 9, SPM images of the scratches for both thin
lms are presented (AFM images are presented elsewhere [13]).
The Co3O4 lms were uniformly grain distributed with, however enlarged grains, probably due to high deposition temperature
[7]. The mean surface roughness (RMS) deviation of the lms
deposited at 450 1C was of the order of 5.5 nm, with the mean
height being around 17.5 nm. On the contrary, the Co lms
originating from Co2(CO)8 presented an extremely smooth surface
with a mean surface roughness around 2 nm and an average
height of about 12.5 nm.
It should be noted that friction anisotropy is actually a phenomenon with two degrees of freedom since one can vary either
the relative orientations of the crystal lattices or the direction of
shearing with respect to the crystal lattices. In literature, the
shearing direction is xed with respect to one surface lattice and
rotation of the crystal lattices with respect to one another (this
experiment could reveal the possible effects of surface lattice
commensurability) [14]. Rotating the shearing direction while
maintaining the relative surface lattice orientations is an equally
challenging experiment in nanoscale (already performed in
macroscale).

4. Conclusions
In the present study, nanoindentation and nanoscratch techniques are utilized in order to investigate the nanomechanical (i.
e. H and E) and nanotribological properties of CVD Co and Co3O4
thin lms, which are widely used in applications for innovative

E.P. Koumoulos et al. / Tribology International 82 (2015) 8994

Normal Load (N)

0

100

200

Normal Load (N)

30 0

400

500

100

200

300

LcU1 =150 N

20

20
0

Displacement (Z) (nm)

surface

-20

post-scratch

-40
-60
-80
-100

Co

-120

500

LcU2 =290 N

post-scratch

-20
-40
-60

LcL =150 N

-80
-100

Co3O4

-120

Scratch direction

400

surface

40

40

Displacement (Z) (nm)

93

scratch direction

-140

-140
-6

-4

-2

-6

Scratch path (nm)

-4

-2

Scratch path (m)

Fig. 8. Nanoscratch depth prole for (a) Co and (b) Co3O4 thin lm, tested with ramping normal load 0.2500 .

Fig. 9. SPM images of the scratch tracks (10 m) for Co thin lm (a) and Co3O4 thin lm (b).

sensing and data storage devices due to their useful properties.

The H and E values are in good agreement with similar measurements in the literature. A wear analysis based on the H/E ratio has
been also performed. The Co3O4 thin lm exhibits higher resistance to wear in comparison to the Co thin lm, a fact that is
conrmed by the nanoscratch analysis showing lower coefcient
of friction for the Co3O4 thin lm compared to the Co thin lm.
Furthermore, nanoscratch depth proles have been performed
for maximum normal load of 500 . The deformation of the
lms is mainly plastic all over the scratch path. For the Co thin
lm, an increase in displacement during post-scratch is observed
which can be attributed to shear stresses that induce a late
recovery of deformation of the thin lm in comparison to the
substrate. A critical load of 150 can cause a limited delamination of the Co3O4 thin lm. The load values, corresponding to the
point where the Co3O4 thin lm fails during post-scratch, are
around 150 and 290 N.

Acknowledgments
The authors wish to acknowledge NTUA funded project for
basic research PEVE-NTUA-2010/65187900 and Alexandros S.
Onassis Public Benet Foundation for the support of this work.

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