Ceramics Material processes II

Coatings Molybdenum Disulfide (MoS2) technique using physical vapor

deposition (PVD).
Adrian Cristian Hidalgo
"School of Materials Engineering, Universidad Del Valle, Cali, Colombia"
Summary
Assisted in plasma, physical vapor deposition (PVD) processes can provide alternative
approaches for the synthesis of two-dimensional (2D) materials such as Molybdenum
Disulfide (MoS2). The main objective of the studies carried out is the deposition of
molybdenum disulfide evaluating its behavior against the tribological properties by making
variations in the parameters of the film deposition process as object / substrate distance,
substrate type temperature and Argon gas pressure. In general, Molybdenum disulfide
(MoS2) is applied with emphasis on tribological mechanisms to reduce fiction and wear.

Keywords: film, Molybdenum disulfide, Coating Processes, Param, cathode substrate,

Magnetron Sputtering, friction.

Introduction operate in more demanding conditions

Throughout history, different materials
such as parts of machines and cutting
tools due to demanding work conditions,
have been exposed to wear phenomena
which have been in constant study
because their incidence causes a life to
be generated Useful reduced of this type
of elements.
The evolution of materials science has
allowed progress on the subject with the
development of new technologies
increasingly sophisticated, such as thin
films which have allowed this type of
machine elements and cutting tools to
and with a longer life. This type of
technology has not only been focused on
the study of wear of materials but has
also been applied in multiple areas, thus
promoting the development of new
techniques to facilitate the deposition of
thin films that can be of an endless
number of materials or elements. Some
of the most common techniques for the
deposition of thin films are PVD, CVD,
PLD, Sputtering among others, each
providing different characteristics or
properties to the film.
As for coatings that contribute to the
tribological properties, it should be noted
that a large number of films made of
different materials have been found. One
of them mentioned in this article of
systematization is Molybdenum Disulfide
(MoS2), which is a solid laminar lubricant
that thanks to its structure provides
protection to wear in difficult working
conditions and resistance to abrasion.
However, the fundamental problem of the
use of (MoS2) is the deterioration of its
tribological properties in a humid
environment, this being a fundamental
point of study for researchers. [1]
Theoretical framework
One of the most used deposition methods
to make coatings is the physical vapor
deposition (Physical Vapor Deposition).
The principle consists of vaporizing
atoms or molecules of a solid material so
that later they are condensed on a
substrate forming a thin layer. For this,
the solid material undergoes a process of
thermal evaporation, where it is subjected
to a heating until evaporation or is
'pulverized' by an intense bombardment
with charged particles in the form of ions
(cathodic bombing or 'sputtering'). In the
latter case, the ions come from an electric
discharge between two electrodes in the
form of plasma, using an inert gas,
generally Argon, and a controlled
atmosphere to avoid the interaction of
vapor of the material formed with the air.
[2]
On the other hand molybdenum disulfide
(MoS2) is known to be a well-established
solid lubricant for vacuum applications.
The lubricating properties of
molybdenum disulfide are intimately
linked to the type of its crystals,
consisting of sets of laminar structure in
which each atom of molybdenum is
alternated with two atoms of sulfur.
: S: Mo: S: S: Mo:
S
Figure 1. Structural scheme of MoS2
This structure allows a relative ease of
sliding between adjacent planes of sulfur,
resulting in a very low coefficient of
friction. In addition to this main
characteristic, molybdenum disulfide
possesses others, such as thermal
stability and chemical stability; it resists
up to more than 2,000 °C in an inert
atmosphere and is not attacked by the
strongest acids. [3]
Methodology
In the present article of systematization
five investigations were approached
where the process of deposition of
molybdenum disulphide films (MoS2) is
studied by means of the technique of
Steam Physical Deposition (PVD) to see
the growth, the structure and the stability
of the coatings in order to improve the
tribological properties and its behavior
against moisture.
In the first research, "Growth, structure
and stability of MoS2" the process was
carried out in a cathodic sputtering plant
suitable for the industry modified with a
cathode of 99.5% purity on silicon
substrates in the form of wafers, which
were initially cleaned with isopropanol
and dried with nitrogen before the
deposition. The supporting substrate
maintained approximately ten
centimeters away from the sputtering
target. The temperature of the substrate
with which the procedure was carried out
was at room temperature and 400 °C.
The process was carried out under
medium vacuum conditions (2 × 10-3 Pa)
feeding the cathode with a DC power
supply of 10. KW in power regulation
mode. Subsequently Argon was
introduced as a cathodic spray gas with a
pressure of (6 x 10-2 Pa). Finally, the
thickness of the coating was
approximately 100 nm.
The surface morphologies of the thin
films of MoS2 deposited at room
temperature and 400 °C are shown in
Figure 2 a and b.
Figure 2: (a) SEM and (b) AFM images of thin films
deposited MoS2 RT and 400 ° C
Films deposited at room temperature
appear generally smooth and
homogeneous according to the (SEM).
This observation is confirmed by atomic
force microscopy (AFM) images where o
gaps are observed indicating a compact
morphology.
At 400 °C of deposition the surface of the
film appears structured in grains of
nanometric size, visible in both the SEM
and AFM images. In this way the surface
of the film exhibits a greater roughness
generating a nano-granular morphology.
To look at the stability of films deposited
at room temperature and 400 °C, an in-
situ laser annealing was used, [4,5]
together with investigations by Ramman
spectroscopy. After 1 second of exposure
to the laser at 3.5 mW at a spot diameter
of approximately 2 m the film has been
permanently modified, indicating the
development of new intense and
persistent Ramman bands (red spectrum
in Figure 3a) , as well as the appearance
of a dark spot (Figure 3b). The spectrum
that arises from the 3.5 mW laser
irradiation of the film deposited at room
temperature is assigned to Mo oxides by
the disintegration of Mo species that are
oxidized when in contact with humidity.
In contrast, the Raman spectra of films
deposited at 400 ° C largely without when
irradiated by the 3.5 mW laser for 30
seconds (Figure 3 a) and 3 b)) because
being relatively stable under these in-situ
annealing conditions thus being more
stable under environmental conditions.
 the molybdenum disulfide film was done
in a mixed atmosphere of Ar and N2 with
a deposition time of 1640 s.

In the results of this investigation it was

Figure 3: (a) In situ annealing laser Raman spectra of
thin films (MoS2), deposited at RT (lower panel) and
400 ° C (top panel). (b) Reflected light microscopy
images of the surfaces of the deposited film and after
laser annealing to 3.5 mW, correlating respond to (a).
found that the morphology of the MoS2
film is characterized by having a porous
and amorphous microstructure as shown
by the SEM and the HRTEM micrograph
respectively. In addition, the dividing line
is visibly clear between the two layers of
AlCrN and MoS2.

In conclusion it was found that thin films

deposited at room temperature are
amorphous, have a smooth surface and
are easily degraded during laser-induced
annealing in ambient atmosphere. In
contrast, films deposited at 400 °C are Figure 4. The cross-sectional image (SEM)
nano-crystalline and show a nano- of AlCrN + MoS2 coating deposited on the
steel substrate.
granular surface morphology and are
comparatively stable against
degradation. [6]

In the second research "Structure and

tribological properties of thin films of low
friction MoS2" the deposition process
was carried out by sputtering on
austenitic steel substrates X6CrNiMoTi
17-12-2 cilindricos of 35 mm diameter Figure 5. HRTEM micrograph.

and 5mm thickness covered with a seed

layer of AlCrN at a temperature of 80 °C.
The process was carried out in vacuum
conditions, bombarding the chamber with
a base pressure below (5x10-5 Pa). Next,
the substrates were cleaned by argon
ions at a pressure of 2 Pa with a
polarization voltage of 600 V / 400 V for
20 min. Subsequently, the deposition of
For the determination of the tribological
properties, it was carried out by the ball-
on-disk method. The friction curve has an
initial transition state during which the
coefficient of friction is reduced together
with the growth of the distance until
obtaining the stabilized state, which
normally occurs after a distance of about
100 m. In this way, under technically dry
friction conditions the registered
coefficient of friction stabilizes in the
range of 0.4-0.5 which is a suitable range
as seen in figure 6.
Figure. 6. dependence of friction coefficient on the
sliding distance during the wear test for AlCrN + MoS2
coating.
In conclusion, the dense microstructure
of the coating was observed without any
visible delamination of the layers as a
whole (AlCrN + MoS2) in the SEM. In
addition, the tests that use the TEM
confirmed an amorphous character of a
low friction of the MoS2 film, which
technically dry friction conditions, the
coefficient of friction is within the
appropriate range. [7]
The third investigation "Magnetic field
argon ion filtration for the growth of
cathodic sputtering of two-dimensional
MoS2 pulsed magnetron", is focused on
finding precise control in plasma-assisted
growth processes to reduce the
generation of defects under
bombardment of ions.
The following scheme illustrates the
experimental arrangement under study
for the deposition of MoS2 films.
Figure 7. Schematic of the experimental setup for the
characterization of magnetron plasma during film
deposition of MoS2.
Regarding the process, the objective
central axis was directed at an angle of
30 degrees with respect to the surface of
the substrate with a distance of 100 mm
from the target center to the center of the
substrate. A magnetic field coil was
placed coaxial with the substrate table at
a distance of 130 mm directly above it.
The coil had a diameter of 160 mm and
was powered by a DC power supply,
generating a regulated magnetic field
strength of 0 to 7 mT in the center of the
coil, when the coil current is adjusted
from 0 to 5 A, respectively.
The intensity of the magnetic field was
mapped as a function of the coil current
for directions along the surface of the
substrate and along the distance
substrate-magnetron represented with
axes x and r in Fig. 7.
For all experiments, the north direction of
the magnetic field was downward along
the central axis of the coil and a chamber
compatible with an ultra-high vacuum and
filled with 99.999% pure argon at a
pressure of 2.0 Pa. In the same way, the
average power conditions of 60 W, a
pulse frequency of 65 kHz and an inverse
time of 0.4 μs were used.
For the correlations of the plasma
characteristics investigated with the
composition and structure of the 2D MoS2
film, several growth experiments were
performed for selected magnetic coil
configurations. Thermally oxidized silicon
wafers with 300 nm oxide thickness were
used as substrates based on a research
on the growth arrangements of the 2D
MoS2 film [8].
The substrates were heated to 700 ° C
and rotated continuously. Growth times
were set at 20 s to produce films
approximately 2 nm thick over the entire
surface of the wafer.
As conclusions it was found that the
modification of magnetron sputtering
deposition pulsed by the addition of an
adjustable auxiliary magnetic field can
provide a new route for a synthesis of 2D
material.
In such growth assisted by 2D film
plasma, the formation of film defects
under bombardment of ions is one of the
main processing challenges. For the
provided example of MoS2 with argon,
the abundance of ionic Ar and ion double
ionized at the location of the substrate
was measured in orders of magnitude
higher than those of the positive Mo and
S ions without evidence of S negative
ions. There was also no evidence of
MoS2 radicals, which points to the
recombination of the substrate surface as
a mechanism for the growth of the ultra-
thin MoS2 film.
The trajectories of the ionized and neutral
Mo and S species sprayed from the target
surface were also influenced, but to a
different extent. The study shows that the
auxiliary magnetic field can effectively
deflect Ar ions and reduce their
abundance at the location of the
substrate by up to a factor of three.
In addition, the adjustment of the intensity
of the magnetic field can be used to
establish an optimal condition between
the reduction of unnecessary Ar-ion
bombardment and to avoid changes of
kinetic energies of all the ions above the
threshold of 8 eV generation of vacancy
defects of sulfur. For the experimental
configuration of this study, said optimum
condition was found at a 3 A coil current,
generating a field of approximately 0.8-
1.2 mT at the substrate location. The
modification of the magnetron sputtering
process discussed is easily scalable,
provides a possibility of direct growth and
can be extended to the synthesis of 2D
allotropes and other thin nanostructured
materials at the molecular scale. [9]
In the fourth research "The role of
moisture and oxygen in thin films MoS2
deposited by sputtering of RF PVD
magnetron" the behavior of MoS2 films is
studied by PVD with the sputtering
technique with RF power supply.
The process was carried out on silicon
substrates covered with silicon oxide. A
99.99% purity MoS2 cathode or target
was used. The power at the RF source
was 300W. The deposition was carried
out in a vacuum of 0.1mBar and
atmosphere of Ar.
According to other authors suggest that
friction behavior is determined by
physisorbed water at "low temperature"
and by oxidation at "high temperature."
[10,11] Based on this hypothesis, friction
resistance tests were performed at room
temperature. (27 ± 1 ° C) in humid air
(65% RH), dry air (8% RH) and dry
nitrogen at room temperature, and at 75 °
C in humid air.The friction curves are
shown in Figure 8.
Figure. 8. Tribological curves to different environmental
conditions.
In moist air (green curve) MoS2 exhibited
the highest COF and the shortest life. The
COF, after an initial 500 turns during the
filming period, stabilizes at 0.17. After
approximately 104 turns, the COF rises to
0.3, which represents the coating failure.
This value was assumed as a reference
for the other tests in different
environments. The life time was slightly
longer in dry air at room temperature for
the light blue curve. After a shooting
period of approximately 5x103 turns, the
COF stabilizes at 0.08 for 104 turns until
it reaches failure. Under a nitrogen
atmosphere (blue curve) at RT, the COF
was approximately 0.01, very close to the
sensitivity limit of the tribometer (5 mN /
400mn = 0.0125), during 8 hours,
corresponding to 25x103 turns. The
coating did not reach failure, since
approximately only half of the coating had
worn away. The previous results were
checked by profilometry and
spectroscopy
From these tests, it is evident that
humidity drastically influences the MoS2
tribological behavior. In a nitrogen
atmosphere (inert environment), it
showed a coefficient ten times lower than
that obtained in humid air, reaching its
best performances and the dry air at
room temperature represented an
intermediate case.
Taking into account the result of this
experiment, it was found that, even at low
film thicknesses (200 nm), the friction
properties depend to a great extent on
the amount of humidity, which induces
the increase in the coefficient and limits
the useful life of the movie. These results
support the model proposed by Spalvins
and colleagues [12], who attribute the
tribological behavior of this type of film to
the presence of a dense and thin
equiaxial layer, which is formed in the first
stage of deposition. [13]
The latest research "MoS2 coatings
resistant to moisture deposited by
unbalanced magnetron spraying"
discusses the deposition parameters of
molybdenum disulfide coatings to obtain
moisture resistance.
Regarding the parameters of the process,
the deposition of the molybdenum
disulfide coating was performed on steel
substrate 1.3343 (S 6-5-2). The cathode
voltage (600 V to 800 V), the target /
substrate distance (65 mm to 115 mm),
temperature (50 °C to 250 °C) and argon
pressure (0.51 Pa to 0.95 Pa) they were
varied in three different levels according
to table 1. Through this process, 27
coatings with very diverse properties
were achieved. All the measured values
with their standard deviations and the
deposition parameters of the 27 samples
are recorded in Table 2.
In general, coatings that show low rates
of wear in the air also tend to obtain low
wear rates in a vacuum. In samples 2, 10
and 13, a combination of low wear in both
vacuum and air is achieved. The first
resistance tests show that these films
support approx. 450,000 cycles in air until
the film fails (under equivalent test
conditions). In softer coating versions,
abrasive wear and especially plowing
prevail. In addition, the COF apparently
differ between air and vacuum, without
being able to establish a clear
relationship (r = 0.482) between them.
The COF are in the range of 0.112 ±
0.013 to 0.221 ± 0.008 in the air and
between 0.013 ± 0.006 and 0.054 ± 0.003
in the vacuum (Table 2). A combination of
low COF in air and vacuum in sample 20
is measured with an average COF in air
of 0.112 ± 0.013 and a COF in vacuum of
0.022 ± 0.006. However, sample 20
shows comparatively high wear rates
especially in air.
As for the mechanical properties of the
films, all these differ a lot. However,
according to the variables made, the
target / substrate distance, temperature
and argon pressure seem to be the most
important. [14]
Conclusions
Generally, all MoS2 films have good
tribological properties independently of
the substrate to be coated and of the
variation of parameters but not
independently of the aspects or basic
principles of deposition.
In the same way, it was evidenced that
those films deposited at room
temperature have better morphological
properties than those deposited at higher
temperatures. For example, the former
presented a smooth and compact
morphology, whereas those deposited at
a higher temperature have a porous
surface and greater roughness. Likewise,
the behavior against tribological
properties was similar for both cases.
However, a similar tendency was not
found in the coatings against their
behavior against humidity, but it was
possible to find a series of parameters
that generated a better behavior in this
case. Among the parameters we have a
deposition temperature of 250 °C,
deposition pressure of 0.73 Pa, cathode /
substrate distance 90 mm among others.
.
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107
Reading Tables 1 and 2

Table 1. Deposition parameters

table 2. Results of the tribological and mechanical characterization Associated With deposition parameters