lubricants

Review
Solid Lubrication with MoS2: A Review
Mohammad R. Vazirisereshk 1 , Ashlie Martini 1 , David A. Strubbe 2 and
Mehmet Z. Baykara 1, *
1 Department of Mechanical Engineering, University of California Merced, Merced, CA 95343, USA
2 Department of Physics, University of California Merced, Merced, CA 95343, USA
* Correspondence: [email protected]




Received: 13 June 2019; Accepted: 28 June 2019; Published: 2 July 2019


Abstract: Molybdenum disulfide (MoS2 ) is one of the most broadly utilized solid lubricants with a
wide range of applications, including but not limited to those in the aerospace/space industry. Here
we present a focused review of solid lubrication with MoS2 by highlighting its structure, synthesis,
applications and the fundamental mechanisms underlying its lubricative properties, together with a
discussion of their environmental and temperature dependence. The review also includes an extensive
overview of the structure and tribological properties of doped MoS2 , followed by a discussion of
potential future research directions.

Keywords: MoS2 ; solid lubricant; tribology; friction; wear; lubrication; dopant

1. Introduction
With their notable influence on an overwhelming number of natural and technical processes,
friction, wear and lubrication are subjects worthy of intense scientific investigation. Despite their
importance, studying individual aspects of these phenomena (which are influenced by a multitude of
factors including the structural, mechanical, and chemical properties of the involved surfaces) in an
isolated fashion has been a challenging endeavor. Nevertheless, with improved computational and
experimental techniques, tribology (a term coined in the 1960s that describes the study of friction, wear
and lubrication) is now an active field of inquiry, with research groups around the world working on
understanding and utilizing its various aspects [1,2].
Considering that a few percent of the gross domestic product of a developed nation is wasted on
overcoming the negative impacts of friction and wear (in the form of direct loss of useful energy as
well as replacement costs associated with machine components damaged by wear) [3], a major goal
of tribology research involves the design and application of methods to minimize friction and wear
at interfaces in relative motion. Toward this goal, significant effort is spent on (i) understanding the
properties and improving the usefulness of existing lubricants and (ii) coming up with new ways of
lubricating interfaces in a more effective fashion (e.g., by decreasing the coefficient of friction, reducing
the wear rate and improving the lifetime of components).
Liquid lubricants are typically what comes to mind when one thinks of lubrication in an industrial
setting [4]. It is indeed true that oils and greases are conventionally employed in many mechanical
systems for lubrication purposes, mostly due to the robust reduction in friction and wear rate that they
provide, the ease with which they can be replenished and the straightforward manner with which they
can be applied to a variety of surfaces. However, certain operating conditions strictly require the use of
solid lubricants instead [5]. The most common examples involve aerospace/space applications, where
low temperatures preclude the use of liquid lubricants which simply become too viscous for effective
lubrication or may even solidify [6,7]. In fact, most of the technical progress involving solid lubricants
was achieved in the second half of the 20th century, motivated by the advent of the space age. Other

Lubricants 2019, 7, 57; doi:10.3390/lubricants7070057 www.mdpi.com/journal/lubricants

Lubricants 2019, 7, 57 2 of 35

examples of applications for solid lubricants involve dry machining operations, where the use of solid
lubricants on machine tools (mainly for wear reduction purposes) may significantly cut down on the
cost of using large amounts of liquid lubricants, and also the food processing and textile industries,
where contamination by liquid lubricants may pose health hazards [8]. In general, solid lubricants are
suitable for many applications that operate in conditions too extreme for liquid lubrication.
Among solid lubricants currently in use, molybdenum disulfide (MoS2 ) [9] holds special
importance. Being a lamellar solid material that consists of individual atomically-thin planes that can
easily slide against each other, the use of MoS2 as a solid lubricant in modern technology dates back to
the previous century [10]. Like graphite (another lamellar material), MoS2 can be used as a dry lubricant
by itself, as an additive in oils or greases, or as an individual component of a composite coating [2].
Unlike graphite, MoS2 does not require humid environments to perform well and it has indeed
been shown that its lubricative properties improve drastically in oxygen-deficient environments [11].
Combined with its ability to operate reliably in a wide range of temperatures (from the cryogenic
regime to several hundred degrees Celsius), the ability to function effectively in vacuum makes MoS2
a particularly attractive lubricant for aerospace/space applications. Consequently, a great body of
scientific work exists on the synthesis, properties and applications of MoS2 as a solid lubricant and
reviews as well as books on the topic have been published as early as the 1960s (see, e.g., [8,9,12,13]).
However, there is still active research on understanding and improving the lubricative properties of
MoS2 , with some of the recent focus areas being on its incorporation into (nano-)composite coatings
and improving its properties via controlled doping [14,15].
This review provides a focused overview of the tribology of MoS2 in the form of a snapshot of our
current physical understanding of this exciting solid lubricant, with the hope that it could potentially
guide future fundamental work. In alignment with this mindset, we focus specifically on MoS2 by itself
as a solid lubricant and do not cover the rather extensive body of work related to its use as an additive
in oils and greases or its utilization in (nano-)composite coatings. Specifically, Section 2 describes
the structure and synthesis of MoS2 , while Section 3 includes an overview and specific examples of
its applications as a solid lubricant. Section 4 details the fundamental mechanisms of low friction
and wear associated with the material, followed by Section 5 which discusses the environmental and
temperature dependence of its lubricative properties. Section 6 deals with doped MoS2 and, finally,
Section 7 concludes the review by providing a brief summary along with highlights of some of the
emerging research directions for MoS2 as a solid lubricant.

2. Structure and Synthesis

MoS2 belongs to the family of layered two-dimensional transitional metal dichalcogenides (TMDs).
Like graphite and hexagonal boron nitride, its crystal structure consists of covalently bonded sheets,
which form stacks that are held together only by weak van der Waals interactions [16]. It occurs
naturally as the mineral molybdenite, an important Mo ore. Due to the strong bonding in-plane and
weak bonding out-of-plane, mechanical, and other properties are highly anisotropic [17], and the
stacks can be easily sheared. Single-layer or few-layer (i.e., 2D) MoS2 (analogous to graphene) can be
produced and studied individually [18].
MoS2 has several different possible structures (polytypes), depending on the bonding within the
sheets and the stacks of the sheets. While graphite has a single plane of atoms per sheet, in MoS2 each
sheet consists of a plane of Mo atoms sandwiched between two planes of S atoms. The single-sheet
structure can feature trigonal prismatic coordination around Mo, which is the semiconducting 1H
(“hexagonal”) structure, or octahedral bonding, which is the metallic 1T (“trigonal”) phase. 1H and the
ideal 1T each have three atoms (MoS2 ) per unit cell (Figure 1); however, theoretical calculations with
density-functional theory (DFT) [19] and X-ray diffraction (XRD) experiments [20] have shown that in
fact 1T is unstable with respect to distortions. The most commonly reported distorted 1T structure is a
reconstruction that triples the unit cell, known as the 1T0 phase [21].
 vaporize parent elemental solids (in this case, Mo and S) in the presence of a catalytic transport agent
(mostly halogens), which eventually results in the synthesis of bulk MoS2 single crystals [33]. Selective
synthesis of the 2H and 3R polytypes in CVT can be achieved by the proper choice of transport agent
(I2 for 2H, Cl2 for 3R) [33]. Despite the fact that the thermodynamically-favored polytypes of MoS2
(2H2019,
Lubricants and 7,
3R)57have been known for a long time, the metastable 1T polytype was only discovered in the3 of 35
early 1990s, through hydration and subsequent oxidation of alkali-intercalated MoS2 compounds
(most commonly KMoS2) [21].

Figure
Figure 1. Structures
1. Structures of the
of the polytypesofofMoS
polytypes MoS22,, constructed
constructed from
fromthe
theexperimental
experimentalliterature, withwith
literature, the the
conventional
conventional unitunit
cellcell marked
marked forforeach.
each.For
For simplicity,
simplicity, the
theideal
ideal1T1Trather than
rather thethe
than distorted 1T′ is1T0 is
distorted
shown. Mo is gray and S is yellow.
shown. Mo is gray and S is yellow.

Each single-sheet structure can be stacked into a crystal where the next sheet is exactly above
the preceding one (AA stacking), producing the 1H, 1T, and 1T0 polytypes. The naturally occurring
polytypes in molybdenite, however, are only based on the 1H sheet, and show more complicated
stacking [9]. The more common is the 2H structure with 2 sheets per cell in AB stacking, where an S atom
in one layer is above an Mo atom in the layer below [22,23]. The less common 3R (“rhombohedral”)
structure has three sheets per cell with ABC stacking [22,24]. These structures are shown in Figure 1.
Mo-S bond lengths are around 2.4 Å for all polytypes [25]. DFT calculations show only very small
energy differences between the 2H and 3R phases [25]. This insensitivity to stacking, and the low
surface energy for 2H-MoS2 of 47 mJ/m2 = 0.025 eV/cell [26], are indicative of low barriers to sliding
and hence low friction. By contrast, 1T and 1T0 are calculated to be higher in energy by 0.8 eV [25] and
0.5 eV per MoS2 unit, respectively [19].
Lattice parameters and space groups for the polytypes are summarized in Table 1. Nonetheless,
deviations from the pristine bulk crystal are common. Calculations have indicated that S vacancies are
the most favorable defects in this material [27]. Various kinds of MoS2 nanostructures can be produced,
including nanoclusters [28], nanometer-size sheets [29], nanotubes and even inorganic fullerenes [30].
The nanoparticles often show relatively poor crystallinity in XRD [31]. Amorphous or nanocrystalline
MoS2 has also been reported (see, e.g., [32]).
While the 2H and 3R polytypes of MoS2 are found in abundance in nature, their bulk single
crystals can also be synthesized in the laboratory using the method of chemical vapor transport
(CVT), whereby a two-zone quartz furnace is utilized for a duration of multiple days to continuously
vaporize parent elemental solids (in this case, Mo and S) in the presence of a catalytic transport agent
(mostly halogens), which eventually results in the synthesis of bulk MoS2 single crystals [33]. Selective
synthesis of the 2H and 3R polytypes in CVT can be achieved by the proper choice of transport agent
(I2 for 2H, Cl2 for 3R) [33]. Despite the fact that the thermodynamically-favored polytypes of MoS2
(2H and 3R) have been known for a long time, the metastable 1T polytype was only discovered in
Lubricants 2019, 7, 57 4 of 35

the early 1990s, through hydration and subsequent oxidation of alkali-intercalated MoS2 compounds
(most commonly KMoS2 ) [21].

Table 1. The structures of the three polytypes of MoS2 . In each case, a = b, and the unit cell angles are α
= 90◦ , β = 90◦ , γ = 120◦ . Lattice parameters are reported from XRD studies. The 3R structure also has a
rhombohedral primitive cell with three atoms.

Space Atoms Per XRD Lattice

Polytype Point Group Stacking Properties
Group Conv. Cell Parameters
a = 5.60 Å,
1T0 P3m1 D3d 9 AAAAAA metallic, metastable
c = 5.99 Å [21]
a = 3.16 Å, semiconducting,
2H P63 /mmc D6h 6 ABABAB
c = 12.29 Å [34] naturally occurring
a = 3.17 Å, semiconducting,
3R R3m C3v 9 ABCABC
c = 18.38 Å [34] naturally occurring

Research on 2D materials has accelerated rapidly in the last decade and a half, thanks to the
advent of graphene and the discovery of its exceptional physical properties [35]. Since MoS2 is one
of the layered TMDs, its synthesis/production in 2D form (consisting of single or only a few layers)
has also been a subject of intense research. While mechanical exfoliation (i.e., cleaving) through the
now-famous adhesive tape method [36] or chemical exfoliation via the use of appropriate solvents [37]
and electrochemically-induced bubbling [38] regularly yield 2D MoS2 flakes of exceptional quality,
their lateral size is only limited to a few tens of micrometers and as such, require the establishment of
alternative methods for the synthesis of large-scale 2D MoS2 films for many technological applications.
The most promising method toward that direction is chemical vapor deposition (CVD), which entails
the use of precursor gases flowing over a substrate (e.g., SiO2 [39–41], sapphire [42] or Au [43]) at
elevated temperatures in a furnace, which eventually results in the synthesis of 2D MoS2 sheets. With
proper choice of precursor gases and deposition parameters, the method now allows the wafer-scale
growth and subsequent transfer of high-quality monolayer MoS2 films for use in various promising
applications [44]. Another route toward obtaining 2D films of MoS2 involves thermal decomposition
(i.e., thermolysis) of ammonium thiomolybdate ((NH4 )2 MoS4 ), which has been demonstrated at the
wafer-scale on insulating substrates, with potential use in device applications [45–47].
While 2D MoS2 films are of potential interest as solid lubricants for nano- and micro-scale
mechanical systems, virtually all current applications where MoS2 is utilized as a solid lubricant
involve films/coatings that are significantly thicker (from a few tenths of µm up to a few µm).
Traditional methods of applying MoS2 as a solid lubricant onto solid surfaces include approaches
such as burnishing and spray bonding; on the other hand, the great majority of MoS2 films employed
in modern systems are coated onto target surfaces using physical vapor deposition (PVD) and in
particular, sputtering. Sputtering involves the bombardment of a MoS2 target by a noble gas plasma
in a vacuum chamber, followed by the ejection and eventual deposition of MoS2 particles onto the
target substrate, creating a conformal coating. The main advantages associated with sputtered MoS2
films when compared with those obtained by other methods are improved adhesion to the substrate,
higher density and significantly higher purity (owing to the deposition process taking place under
vacuum), all of which are factors contributing to improved tribological properties including low
coefficient of friction and enhanced wear resistance [8]. Sputtered MoS2 films, which may, in the
as-sputtered state, consist of mainly columnar (with MoS2 crystallites oriented perpendicular to the
substrate) or basal (with MoS2 crystallites oriented parallel to the substrate) morphologies [48], are
utilized both for fundamental studies [49] as well as critical applications, e.g., as solid lubricants
on bearings employed in spacecraft [7,50]. A particular advantage of the sputtering method is that
other materials can be co-sputtered with MoS2 relatively easily in order to achieve doped coatings
with improved properties [15], as discussed further in Section 6. The method of sputtering MoS2
onto the target surface (in particular, the choice of RF (radio frequency), DC (direct current) and/or
Lubricants 2019, 7, 57 5 of 35

magnetron-assisted sputtering, etc.) can also have important implications for the structure and
tribological performance of the resulting films [15]. For example, morphology depends on the
deposition system and deposition temperature [51,52]. It has also been shown that sputtering methods
as well as substrate bias greatly influence the Mo–to–S ratio in both pure and doped coatings [53,54].
Having said this, a detailed discussion of the relationship between the deposition method and the
resulting structure and composition of MoS2 coatings is not part of this review. Finally, it should be
mentioned that alternative methods such as pulsed laser deposition [55] have also been utilized for
MoS2 coatings, although not as widely as sputtering.

3. Tribological Applications of MoS2

Generally, solid lubricants are used when liquid lubricants do not meet the advanced requirements
of a given application. For example, oils or greases cannot be used in many applications because of
issues with application, sealing problems, weight, or environmental conditions [56]. Solid lubricants
also reduce weight, simplify lubrication and, in some cases, are less expensive than oil and grease
lubrication systems [8,56,57]. Table 2 summarizes the conditions and corresponding applications
where solid lubricants can be used to overcome limitations associated with standard greases and oils.
In high or ultrahigh vacuum conditions, liquid lubricants can evaporate such that they are unable
to perform their lubricating function and can potentially contaminate the device. Similarly, liquid
lubricants can decompose or oxidize at high temperatures. At the other end of the spectrum, at
cryogenic temperatures, liquid lubricants can solidify or become too viscous to flow effectively. Under
radiation or corrosive gas environments liquid lubricants can decompose. High pressure applications
can exceed the load carrying capacity of liquids. In cases where contamination is a major issue,
liquid lubricants can be problematic because they tend to pick up dust and other contaminants from
the environment. In applications where weight is of primary importance, liquid lubricants and the
associated components can be too heavy. Lastly, if service is difficult or impossible, it may not be
viable to use a liquid lubricant that degrades over time, particularly if the application experiences long
storage or idle periods. Solid lubricants overcome many of these issues.
Notable in Table 2 is one application where almost all the conditions for poor liquid lubrication exist,
i.e., in space mechanisms. Moving systems in space include vehicles, satellites, telescopes, antennas, and
rovers. Such systems must operate for long periods of time with little or no service under a wide range of
extreme environmental conditions. Since most space applications operate in vacuum environments, the
typical solid lubricant of choice is MoS2 [7,58]. Unlike graphite, which requires sufficient vapor pressure
of water to provide lubrication, MoS2 performs best in vacuum environments [59]. Representative
examples of components in space applications that already rely on MoS2 lubricants are ball bearings,
pointing mechanisms, slip rings, gears, and release mechanisms [15,60]. It has indeed been suggested
that most, if not all, the American satellites and spacecraft contain MoS2 for some application [13].
The continuing interest in the development of solid lubricants (including MoS2 ) for space
applications stems from the fact that planned space missions increasingly involve a wide range of
operating conditions (in particular, in terms of temperature) and longer durations during which the
mechanisms that enable relative motion will need to operate in a robust and reliable fashion without
regular maintenance. A particularly important example highlighting the importance of related efforts
is the catastrophic high-gain antenna deployment failure associated with the Galileo spacecraft [61],
caused by the failure of the MoS2 -based solid lubricant during operation in space that was successfully
tested before deployment on Earth under ambient conditions. In order to meet the requirements
of demanding space missions, basic and applied research is being conducted around the world to
understand and improve the properties of solid lubricants in general and MoS2 -based lubricants in
particular. Illustrative examples of such ambitious missions include NASA’s planned lander mission
to Europa (the surface of which can be below −200 ◦ C) for astrobiology research, as well as ESA0 s
BepiColombo mission to Mercury, where the spacecraft will be exposed to temperatures on the order
of 250 ◦ C [7].
Lubricants 2019, 7, 57 6 of 35

Table 2. Examples of conditions or environments where liquid lubricants are either undesirable or ineffective and solid lubricants can be used, and representative
applications where those conditions exist; adapted from Ref. [56].
Medical or Food Hard Disks, Furnaces/ Bridge, Plant
Space Nuclear Semiconductor Refrigeration/Liquid
Dental Processing Microscopes, Metalworking or Building
Mechanisms Reactors Manufacturing Nitrogen Pumps
Equipment Equipment Cameras Equipment Supports
High
x x
Temperature
Cryogenic
x x
Temperature
Radiation x x
Corrosive
x x
Gas
High
x x x
Pressure/Load
Product
Contamination x x x x
Unacceptable
Service
Difficult or x x
Impossible
Weight
Limited x
Applications
Lubricants 2019, 7, 57 7 of 35

Based on the fact that MoS2 is the most extensively used solid lubricant in space mechanisms,
Lubricants 2019, 7, x FOR PEER REVIEW 8 of 36
a particularly timely example will be highlighted here: the James Webb Space Telescope (JWST),
which is planned
The impressivefor launch in 2021properties
tribological and is theofsuccessor
MoS2 under to the Hubbleand
vacuum Space
in aTelescope.
wide range MoS of 2 has
beentemperatures
determinedmake as the it asolid
natural choice asofa choice
lubricant solid lubricant for applications
for sensitive in space;
mechanisms however,in
employed thea fact
number
that its lubricity
of precision instrumentsrapidlyon deteriorates under humid
JWST, including conditions
the Near represents
Infrared a significant
Spectrograph barrier toand
(NIRSpec) its the
extensive use in demanding terrestrial applications. On the other hand, recent
Mid-Infrared Instrument (MIRI) (Figure 2) [50,62]. Critical to the choice of MoS2 as the preferred developments in solid
coating technology, in particular the use of closed field unbalanced magnetron sputter ion plating
lubricant for these high-precision instruments was the fact that it preserves its lubricative properties
(CFUBMSIP) employed to co-sputter MoS2 with Ti, has resulted in lubricant coatings with notable
down to cryogenic temperatures (which include 30 K, the temperature around which JWST will be
improvement in mechanical properties and resistance to humidity [65–67]. These improvements
operating)
resulted[63]in and the high uniformity
the successful use of MoS2with
-basedwhich it can
coatings in be
drydeposited
machiningonoperations,
precision such
bearings employed
as cutting
in theand
instruments
forming, as well as certain machine components that do not operate under vacuum conditions. the
at sub-micron thicknesses, ensuring stable operation. In order to minimize
chances of athese
Despite lubricant-related
developments,catastrophic
it is projectedfailure
that theafter
maindeployment
use of MoS2 (like thelubricant
as solid Galileo),will
a significant
be in
amount of work hasapplications
aerospace/space been performed for thetoforeseeable
characterize the tribological
future, with ongoingperformance
fundamentalofandbearings
appliedunder
research
various directed
operating at adjusting
conditions onthe properties
earth of MoS
and it has 2 coatings
been towardthat
determined long-term missions
a run-in and a performed
procedure wider
range of operating conditions.
under vacuum is necessary to ensure low-friction torques for eventual use in space [64].

Figure
Figure 2. (a)2.The
(a) The filter
filter wheel
wheel assemblyof
assembly ofthe
the MIRI
MIRI instrument
instrumentonon thethe
JWST; (b) (b)
JWST; A bearing employed
A bearing employed
in the filter wheel assembly; (c) The MoS2 -coated bearing race featured in the bearing.and
in the filter wheel assembly; (c) The MoS 2 -coated bearing race featured in the bearing. (a) (a) (b)
and (b)
reproduced
reproduced fromfrom [50]
[50] withSPIE
with SPIE permission.
permission. (c) (c)
Republished with permission
Republished of IOP Publishing
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Before concluding
The impressive this section,
tribological properties it needs
of MoSto2 under
be mentioned
vacuum and that in MoS 2 has numerous other
a wide range of temperatures
applications besides lubrication that are not covered in this review. One of the most important is
make it a natural choice as a solid lubricant for applications in space; however, the fact that its lubricity
heterogeneous catalysis, in which active sites are edges, defects, or near “promoter” dopants (Ni, Co).
rapidly deteriorates under humid conditions represents a significant barrier to its extensive use in
MoS2 can catalyze reactions including hydrodesulfurization, hydrogen evolution reaction, oxygen
demanding
reduction terrestrial
reaction, applications. On the
and photo-catalytic other
water hand,[68].
splitting recentThedevelopments
ability of MoS2 in coatingLitechnology,
to absorb between in
particular the (intercalation)
its layers use of closed has fieldbeen
unbalanced
utilized formagnetron sputter
batteries [68]. ion plating
Electronic (CFUBMSIP)
and optical employed
applications have to
co-sputter
become MoS 2 with Ti,focus
a particular has resulted in lubricant
after the advent coatings
of few-layer MoSwith notable
2, which haveimprovement
been reviewedinrecently
mechanical
properties
[18,69].and resistance
Some to humidity
unique features [65–67].
are strong Theseeffects,
excitonic improvements resulted band-gap
a direct-to-indirect in the successful
transitionuse of
MoS2 -based coatings in dry machining operations, such as cutting and forming, as well asThe
with number of layers, tunability by strain, and ease of creating heterojunctions by stacking. certain
presence
machine of multiple
components thatinequivalent
do not operate low-energy valleys conditions.
under vacuum in the bandDespitestructure might
these be used in it is
developments,
“valleytronics”,
projected and the
that the main usestrong
of MoSspin-orbit coupling suggests spintronic applications. These properties
2 as solid lubricant will be in aerospace/space applications for the
have been explored for use in transistors, sensors, photovoltaics, light-emitting diodes, and lasers
foreseeable future, with ongoing fundamental and applied research directed at adjusting the properties
[18,69].
of MoS2 coatings toward long-term missions and a wider range of operating conditions.
Before concluding
4. Mechanisms of LowthisFriction
section,andit needs
Wearto be mentioned that MoS2 has numerous other applications
besides lubrication that are not covered in this review. One of the most important is heterogeneous
While MoS2 has been known to be a good solid lubricant for many years [12], the mechanisms
catalysis, in which active sites are edges, defects, or near “promoter” dopants (Ni, Co). MoS2 can
through which this performance is achieved have been a subject of ongoing research. This section
catalyze
will reactions
provide anincluding
overview hydrodesulfurization,
of experimental and computationalhydrogen evolution
efforts aimed reaction, oxygen reduction
at understanding the
reaction, and photo-catalytic water splitting [68]. The ability
physical reasons behind the extraordinary lubricity of this lamellar material.of MoS 2 to absorb Li between
Moreover, key resultsits layers
(intercalation) has been
of atomic force utilized
microscopy for batteries
(AFM) [68].studies
based friction Electronic
on 2Dand MoSoptical
2 samples applications
(which onlyhave become
consist of a
particular
a singlefocus
layerafter
or a the
few advent of few-layer
layers stacked on top ofMoS 2 , which
each have
other) will bebeen reviewed recently [18,69]. Some
reviewed.
The most
unique features arewidely-referenced
strong excitonic effects,works in the literature aimed
a direct-to-indirect at elucidating
band-gap transitionthe with
lubricative
number of
properties of MoS 2 are the detailed transmission electron microscopy (TEM) studies by Martin et al.
layers, tunability by strain, and ease of creating heterojunctions by stacking. The presence of multiple
that werelow-energy
inequivalent performed in the early
valleys in the1990s
band[49,70]. Whilemight
structure techniques suchinas“valleytronics”,
be used XRD have been employed
and the strong
before to understand some aspects of the friction mechanisms related to MoS2 coatings [71], the TEM
spin-orbit coupling suggests spintronic applications. These properties have been explored for use in
transistors, sensors, photovoltaics, light-emitting diodes, and lasers [18,69].
Lubricants 2019, 7, 57 8 of 35

4. Mechanisms of Low Friction and Wear

While MoS2 has been known to be a good solid lubricant for many years [12], the mechanisms
through which this performance is achieved have been a subject of ongoing research. This section will
provide an overview of experimental and computational efforts aimed at understanding the physical
reasons behind the extraordinary lubricity of this lamellar material. Moreover, key results of atomic
force microscopy (AFM) based friction studies on 2D MoS2 samples (which only consist of a single
layer or a few layers stacked on top of each other) will be reviewed.
The most widely-referenced works in the literature aimed at elucidating the lubricative properties
of MoS2 are the detailed transmission electron microscopy (TEM) studies by Martin et al. that were
performed in the early 1990s [49,70]. While techniques such as XRD have been employed before to
understand some aspects of the friction mechanisms related to MoS2 coatings [71], the TEM images
provided convincing visual evidence for the processes by which MoS2 was thought to exhibit low
friction and wear [49,70]. In particular, by performing pin-on-flat tribometer experiments under
ultrahigh vacuum conditions on sputter-deposited, stoichiometric, polycrystalline MoS2 films followed
by TEM imaging of the wear debris as well as the film itself, the following key processes were
determined to take place during relative sliding motion between components lubricated by MoS2 :

(1) The establishment of a transfer film on the counter-surface as it slides against the
MoS2 -coated component.
(2) The shear-induced orientation of the basal planes of MoS2 (in the original coating, the transfer
film and eventually in third bodies/wear particles) in the sliding direction.

Careful study of the Moiré patterns that emerge during TEM imaging showed that a key feature
leading to ultra-low friction (often referred to as superlubricity [72], with friction coefficients on
the order of 0.001) of MoS2 coatings is significant variability in the rotational registry of individual
MoS2 crystallites around the surface-normal direction (Figure 3). This leads to a rotational structural
mismatch between basal plane pairs that come into contact with each other at the interfaces that
form between the original coating, the transfer film and the third bodies, leading to a systematic
cancellation of atomic-scale lateral forces. This results in the establishment of an ultra-low friction
regime, in agreement with the theory of structural superlubricity that was spearheaded by Hirano [73]
and Sokoloff [74], and is still being investigated in many different experimental systems [72].
Even though the pioneering TEM works described above pinpoint structural superlubricity
between basal planes of MoS2 as the main reason for its ultra-low friction characteristics, a particular
limitation involves the inability to directly observe, in an in situ fashion, the sliding process between
the layers and to directly measure the shear forces that take place during sliding. These shortcomings
were partially addressed in a careful experimental study performed by Oviedo et al., where two custom
cross-sectional TEM setups were used to (i) visualize in situ with high-resolution the sliding between
individual basal planes of MoS2 (Figure 4) and (ii) quantify the shear strength of the interface between
the layers [75]. In particular, the upper bound for the shear strength was determined (by focusing on
interlayer sliding between MoS2 layers in commensurate registry) to be 24.8 ± 0.5 MPa. In another
important work, utilizing a mechanical force sensor in the form of a silicon nanowire inside a scanning
electron microscope (SEM), an individual, single-layer flake of MoS2 was controllably detached from
and slid on its bulk parent MoS2 substrate in structurally incommensurate registry [76]. In what
constituted the first direct measurement of friction forces between incommensurate basal planes of
MoS2 , the authors obtained an ultra-low friction coefficient on the order of 0.0001 (well within the
superlubric regime [77]), supporting the original proposition by Martin et al. that easy-shear sliding
between incommensurate basal planes of MoS2 is responsible for its ultra-low friction. In yet another
rather challenging experimental study, AFM tip apexes were intentionally wrapped with sheets of
2D materials (including MoS2 ) and slid on a bulk graphite substrate, with experimentally-recorded
friction coefficients smaller than 0.002 [78].
Lubricants 2019, 7, 57 9 of 35
Lubricants
Lubricants 2019,
2019, 7,
7, xx FOR
FOR PEER
PEER REVIEW
REVIEW 10
10 of
of 36
36

Figure
3. A3. A
A high-resolution
3.high-resolution TEM
high-resolutionTEM image
image obtained
TEM image obtained on MoS
onon MoS2 wear debris that shows the existence of two
Figure
Figure obtained MoS 2 wear
2 wear debris
debris that shows
that shows the existence
the existence of two of
separate
separate MoS
MoS 2 planes with different rotational registry on the underlying MoS2 region. Figure
planes with different rotational registry on the underlying MoS region.
two separate MoS2 planes with different rotational registry on the underlying MoS2 region. Figure
2 2 Figure
reprinted
reprinted from [[70]
70] with permission from Elsevier.
reprinted fromfrom
[70] withwith permission
permission fromElsevier.
from Elsevier.

Figure 4. High-resolution, cross-sectional TEM images obtained sequentially over the course of a
Figure 4. High-resolution, cross-sectional TEM
TEM images
Figure 4. High-resolution, cross-sectional imagesobtained
obtainedsequentially
sequentiallyoverover
the course of a of a
the course
minute
minute as an
an oxidized
as oxidized
oxidized tungsten tip
tip is
tungsten tip is used to controllably shear off
off aa single layer
layer of MoS22 from
MoS aa nine-
minute as an tungsten isused
usedtoto
controllably
controllablyshear
shear single
off a single oflayer from
of MoS nine-
2 from a
layer
layer sample.
sample. Adapted
Adapted with
with permission from [[75]
permission from 75] ,, copyright
copyright 2015
2015 American
American Chemical
Chemical Society.
Society.
nine-layer sample. Adapted with permission from [75], copyright 2015 American Chemical Society.
Due to experimental difficulties associated with the measurement of friction forces between
Due Due to experimental
to experimental difficultiesassociated
difficulties associated with
with the themeasurement
measurement of of
friction forces
friction between
forces between
individual
individual MoSMoS22 planes
planes in
in an
an isolated
isolated fashion
fashion andand the
the requirement
requirement of of highly
highly customized
customized setups
setups that
that
individual
are MoS2 planes in an isolated fashion and the requirement of highly customized of setups that
are not
not readily
readily accessible,
accessible, computational
computational efforts
efforts play
play an an important
important role
role in
in the
the elucidation
elucidation of low
low
are not readily accessible,ofcomputational
friction efforts play an important role in theindividual
elucidation of2low friction
friction mechanisms
mechanisms of MoS MoS22.. Importantly,
Importantly, simulations
simulations of of sliding
sliding between
between individual MoS MoS2 sheets
sheets
mechanisms
based
based on of MoS
on molecular
molecular . Importantly,
2 dynamics
dynamics (MD) simulations
(MD) have
have uncovered of sliding
uncovered (i) between
(i) aa 100-fold individual
100-fold decrease
decrease in MoS
in friction sheets
friction force
2
force when based
the on
when the
molecular
sheets dynamics
sheets are
are rotated (MD)
rotated with
with haveto
respect
respect uncovered
to each
each other (i)transition
other to
to a 100-fold
transition from
fromdecrease in friction
aa commensurate
commensurate to force
to an
an when the sheets
incommensurate
incommensurate
are rotated with respect to each other to transition from a commensurate to an incommensurate state;
(ii) that the highest energy barriers to sliding are located on top of S atoms; and (iii) that Coulombic
repulsion between the layers plays an important role in the easy shear characteristics, supplementing
Lubricants 2019, 7, 57 10 of 35

the reduction in energy barriers to sliding that is induced by structural mismatch [79,80]. A subsequent
study based on DFT focused on the load-dependence of friction between individual MoS2 planes
by simulating potential energy landscapes, and determined that inter-layer friction increases with
increasing load based on electrostatic effects [81]. Another study of inter-layer motion using both DFT
and MD showed that the energy barriers to sliding in MoS2 are larger than those of other 2D materials
(graphene and boron-nitride) due to the corrugated nature of the MoS2 surface, which increases both
the dispersion binding and the energy barriers, and also because the sulfur anions are more polarizable
than the first-row atoms in graphene and boron-nitride [82].
The main characteristics that make MoS2 a low-friction material (in particular, the ability of its
basal planes to orient in the direction of sliding) are also mainly responsible for its wear-resistant
properties. TEM-based studies performed on MoS2 films deposited by CVD have established that
mechanical properties including strength, elastic modulus and strain to fracture improve during the
initial stages of sliding, accompanied by a marked decrease in wear rate [83]. The physical mechanism
behind the in situ enhancement of mechanical properties and thus, wear resistance, is thought to
involve an interplay of film densification (induced by individual crystallites pushing into the pores
in the as-synthesized films under contact stresses) and the ability of the MoS2 crystallites to easily
re-orient themselves in the direction of sliding to accommodate shear strain and delay the onset of
fracture that would eventually manifest as wear [83,84]. The wear resistance of pure MoS2 films can be
further augmented by the use of dopants [85], as described in Section 6.
It is also important to note that the tribological behavior of MoS2 depends on the test conditions,
as reflected in the stability and thickness of the generated tribofilm. The properties of the tribofilm are
determined by the conditions at the interface and so are intrinsic to the tribological system. Therefore,
one approach to understanding the tribological mechanisms of MoS2 is to analyze the transfer film.
This has been done, for example, using techniques that involve stylus-based roughness measurements
on the counterface [86] or using approaches based on digital microscopy to characterize tribofilm
evolution [87,88].
The invention of the AFM [89] and the realization that it can be used to study frictional properties
on the nanometer scale [90], opened up a new era in tribology research where friction could, for
the first time, be studied at the “single asperity” level, with the potential to provide fundamental
physical information about this ubiquitous phenomenon. Moreover, the realization that graphene can
be readily obtained from its lamellar bulk form by simple mechanical exfoliation [91] and the booming
interest in related 2D materials that followed, resulted in a number of AFM-based studies regarding
the frictional properties of such materials. The motivation to study the frictional properties of 2D
materials is mainly based on the desire to establish robust and effective lubrication schemes for nano-
and micro-scale mechanical systems, where increasing surface-to-volume ratios amplify surface effects
(e.g., surface tension, stiction) that preclude the use of liquid lubricants and lubrication via thick layers
of lamellar solids is generally impractical because of geometric constraints associated with the size of
the components.
At this point, it should be emphasized that AFM-based friction studies on 2D materials (including
MoS2 ) probe mechanisms and properties that are fundamentally different from those that are largely
responsible for the lubricity of such materials in their bulk form. In particular, while the excellent
frictional properties of MoS2 have been mainly attributed to easy shear between its basal planes and
related processes as discussed above, no interlayer shear takes place during AFM experiments, where
the measured friction forces occur at the interface between the AFM tip and the top surface of the
MoS2 sample. Based on this, it is perhaps surprising that AFM-based studies of friction on such
materials still reveal miniscule friction forces and drastically decreased friction when compared with
typical substrates (e.g., SiO2 ) on which they are deposited. As no interlayer sliding takes place during
experiments that feature a few-layers of material (and interlayer sliding is, by definition, not possible
for single-layer samples), the significant lubricative properties of 2D materials in AFM experiments are
Lubricants 2019, 7, 57 11 of 35

Lubricants 2019, 7, x FOR PEER REVIEW 12 of 36

attributed to other physical factors [92], including their (i) atomic-scale smoothness; (ii) mechanical
strength and experiments
in AFM (iii) chemicalare inertness.
attributed to other physical factors [92], including their (i) atomic-scale
smoothness; (ii) mechanical
Despite the fact that the great strength and (iii)
majority ofchemical
AFM-based inertness.
nanotribological studies on 2D materials
have been performed on graphene, single- or few-layer nanotribological
Despite the fact that the great majority of AFM-based MoS2 have alsostudies been on the2Dtarget
materials
of some
have been performed on graphene, single- or few-layer MoS 2 have also been the target of some recent
recent experimental work. Although AFM-based friction measurements on single-layer MoS2 have
experimental work. Although AFM-based friction measurements on single-layer MoS2 have been
been performed as early as 1996 [93], the first systematic, comparative report of AFM-based friction
performed as early as 1996 [93], the first systematic, comparative report of AFM-based friction
measurements on 2D materials (which also includes results obtained on mechanically exfoliated
measurements on 2D materials (which also includes results obtained on mechanically exfoliated
flakesflakes
of single- andand
of single- few-layers
few-layers ofof
MoS
MoS2 )2)appeared
appeared in in 2010
2010[94].
[94].Specifically,
Specifically, it was
it was observed
observed that the
that the
magnitude
magnitude of friction measured on MoS2 (deposited on SiO2 substrates) decreased monotonically with
of friction measured on MoS 2 (deposited on SiO 2 substrates) decreased monotonically
increasing number ofnumber
with increasing layers (until a total
of layers ofa~5
(until layers
total of ~5was reached,
layers see Figure
was reached, 5). The5).
see Figure authors attributed
The authors
the consistent
attributedbehavior of decreasing
the consistent behaviorfriction with increasing
of decreasing friction withnumber of layers
increasing to a mechanical
number of layers toprocess
a
calledmechanical
puckering,process
whereby called
thepuckering,
AFM tip apexwhereby thatthe AFMthe
probes tip 2D
apex that probes
samples the 2D
creates samples
locally createsareas
deformed
locallyaround
(puckers) deformed areas
itself, (puckers)
which aroundfriction
increases itself, which
due toincreases frictionindue
an increase to an increase
contact area. As in the
contact
number
area. As the number of layers increases, the bending stiffness of the 2D material in the vertical
of layers increases, the bending stiffness of the 2D material in the vertical direction also increases,
direction also increases, leading to a decrease in puckering and consequently, in friction. While
leading to a decrease in puckering and consequently, in friction. While factors, such as electron-phonon
factors, such as electron-phonon coupling [95] as well as surface roughness [96], may also play a role
coupling [95] as well as surface roughness [96], may also play a role in the layer-dependent friction of
in the layer-dependent friction of 2D materials, the puckering phenomenon is generally accepted to
2D materials, the puckering
be the dominant mechanism. phenomenon is generally accepted to be the dominant mechanism.

FigureFigure
5. (a)5.Friction
(a) Friction
mapmap acquiredby
acquired byAFM
AFMon on an
an MoS
MoS22flake
flakefeaturing regions
featuring of single-layer
regions (1L), (1L),
of single-layer
three-layer
three-layer (3L) bulk
(3L) and and (BL)
bulkthickness.
(BL) thickness.
BrighterBrighter colors indicate
colors indicate higher friction
higher friction values; values; (b)
(b) Normalized
Normalized
friction friction
as a function ofasnumber
a function of number
of MoS of MoS
layers for 2 layers for three different samples, whereby a
three different samples, whereby a decrease in
2
decrease in friction with increasing number of layers is observed. The friction map in (a) corresponds
friction with increasing number of layers is observed. The friction map in (a) corresponds to Sample 1
to Sample 1 in (b). Reprinted from [94] with permission from AAAS.
in (b). Reprinted from [94] with permission from AAAS.
Recent work performed on polycrystalline, single- to few-layer MoS2 samples grown by CVD
Recent work performed on polycrystalline, single- to few-layer MoS2 samples grown by
featuring grains up to a few hundreds of nanometers in size revealed a strikingly different layer-
CVDdependence
featuring grains up to
of friction a few
than hundreds
single of nanometers
crystal samples obtainedinbysize revealedexfoliation
mechanical a strikingly
[97].different
In
layer-dependence of friction than single crystal samples obtained by mechanical exfoliation
particular, under ambient conditions, the layer dependence was found to be of an “oscillatory” [97]. In
particular, under ambient conditions, the layer dependence was found to be of an “oscillatory” nature,
whereby samples with odd numbers of layers exhibited higher friction relative to those samples with
Lubricants 2019, 7, 57 12 of 35

even numbers of layers. This rather interesting result was attributed to a mechanism involving the
enhanced adsorption of charged species at samples with odd numbers of layers due to the existence of
permanent dipoles. The adsorption of such species changes the interactions of the sample surface with
the probing tip apex, ultimately leading to enhanced friction when compared with samples featuring
even numbers of layers [97].
In AFM experiments, it is widely observed that the physical properties of the tip apex have a
profound effect on the recorded data. This observation is also true for AFM-based investigation of
friction mechanisms on MoS2 , as it has been recently shown that layer-dependent friction on 2D MoS2
becomes strongly non-monotonic (first decreasing when switching from one to two layers, and then
progressively increasing with increasing number of layers) when probed with blunt, pre-worn tips [98].
These results point to the conclusion that the physical properties of individual sliding components,
in addition to those of the solid lubricant, need to be carefully evaluated in the design of small-scale
mechanical systems to achieve adequate lubricative performance.
The anisotropy of friction on MoS2 is another topic that has been investigated via AFM on 2D
samples. Specifically, Cao et al. determined, by means of consecutive friction measurements performed
on MoS2 flakes gradually rotated with respect to the AFM scanning direction, that the friction forces
on MoS2 exhibit anisotropic behavior with a periodicity of 180◦ [99]. This observation is surprising at
first glance, as a periodicity of 60◦ would have been expected based on crystal symmetry. Inspired by
previous anisotropy work on graphene [100], the authors attributed their observations to the existence
of parallel ripples in the MoS2 samples induced by in-plane strain that occurs during the deposition
of the samples on the SiO2 substrate in conjunction with the puckering effect, which leads to the
emergence of high- and low-friction sliding directions (separated by 90◦ ) that correspond to the tip
moving across or along the ripples, respectively. While the work by Cao et al. also discusses the effect
of sample thickness and load on friction anisotropy in a convincing fashion, the specific role played by
the AFM tip apex (for instance, by its size and stiffness) in friction anisotropy remains to be studied in
future work.
The frictional properties of 2D MoS2 have been recently compared with those of graphene [101],
employing samples grown by CVD, which provides films of lateral sizes that are much more suitable
for practical purposes than those obtained by mechanical exfoliation. By combining AFM-based
imaging and micro-tribometer tests, it was determined that the MoS2 film exhibited superior friction
and wear characteristics when compared with graphene. The authors attributed this observation to
the fact that MoS2 is directly grown on the SiO2 substrate employed in the measurements, whereas
graphene needs to be grown on copper foils first and then transferred onto SiO2 through chemical
means. This process inevitably introduces contaminants, which prevent intimate contact and adhesion
between graphene and the underlying substrate, ultimately leading to inferior friction and wear
performance [101]. This result is in contrast to another recent direct comparison between MoS2 and
graphene conducted via AFM measurements of both materials in the same scan line that showed
graphene consistently exhibited lower friction. The experimental results were analyzed using DFT and
MD simulations, which revealed the mechanism underlying the friction contrast to be a higher energy
barrier to sliding on MoS2 [102]. These studies will almost certainly encourage future comparisons
between 2D materials which will highlight their strengths and weaknesses and inform their use in
specific applications.

5. Environment and Temperature Dependence

The tribological behavior of MoS2 is extremely sensitive to environmental conditions. As stated
before, one of the main prerequisites to achieve ultralow friction with MoS2 lubricants is the absence
of contaminants, such as oxygen, water, and hydrocarbons [49]. Among the first observations of
the environmental dependence of the lubricative properties of MoS2 , Peterson and Johnson [103]
showed in 1953 that the friction between metal surfaces lubricated by MoS2 increased with relative
humidity (R.H.) up to 65% and then decreased. After this work, the presence of water and various
Lubricants 2019, 7, 57 13 of 35

forms of oxygen was shown to increase friction and wear in several studies [104–108]. In the following,
we summarize the effect of oxygen and then water on the friction and wear behavior of MoS2 as a
solid lubricant.
The presence of molecular and atomic oxygen can lead to surface-limited oxidation (or
near-surface-limited, due to the subsequent protection that occurs via the oxidation layer) of MoS2
films, significantly affecting their tribological performance. The oxidized layers of MoS2 films can
cause high friction during the run-in process; then, once the initial oxide has been removed, the friction
drops to its low steady-state value as long as the oxide removal rate is higher than the oxidation
rate in the system [109,110]. This high friction run-in regime can cause problems particularly in
aerospace and satellite devices in which operation is infrequent and oxidation can occur by molecular
oxygen during the assembly and testing of a device on earth [111]. Oxidation may also happen in the
presence of atomic oxygen, which is extremely reactive and quickly oxidizes the surface of MoS2 [112],
particularly during operation in the low earth orbit (LEO) environment (altitudes of 100–1000 km). The
pre-operation exposure to the terrestrial environment before space missions enhances the premature
failure risk in satellite devices. The failure of the high gain antenna in the Galileo spacecraft is an
example caused by this problem, whereby the failure of bearings during deployment was attributed to
the prolonged storage and transportation of the components [113].
Molecular oxygen was shown not to affect the tribological properties of MoS2 at room
temperature [109,114]; however, it can oxidize the MoS2 edge sites at high temperature, whereby
MoO3 (and MoO2 ), as a product of this oxidation, disrupts the easy shear properties of the MoS2
lubricant film and creates high wear [115]. The oxidation of MoS2 starts with the physisorption
of oxygen on the surface of MoS2 and then the chemical formation of Mo oxides. MoS2 oxidation
increases with an increase in temperature [116]. The transition temperature at which the oxidation
rate increases substantially has been reported to be from 100 [117,118] to 400 ◦ C [119,120], which
may depend strongly on the preparation method of the MoS2 film and on film conditioning induced
by deliberate thermal cycling during sliding prior to testing [109]. In general, powdered coatings
(i.e., mechanically deposited coatings) exhibit higher transition temperatures compared to sputtered
coatings, which might stem from (i) larger grain sizes in the mechanically deposited films which
decrease the susceptibility to oxidation and/or (ii) the porous structure of the sputtered films which
can speed up the oxidation of MoS2 as a result of tribochemical reactions [109,119,121,122]. The effect
of microstructure on tribological performance of MoS2 coatings under ambient environment was
further studied by comparing the friction of highly oriented N2 -spray-deposited MoS2 films and
amorphous films produced via DC magnetron sputtering [123,124]. Highly-ordered MoS2 films with
surface-parallel basal orientation exhibited higher resistance to oxidation compared to amorphous
MoS2 films. Moreover, X-ray photoelectron spectroscopy (XPS), and high-sensitivity low-energy ion
scattering (HS-LEIS) analysis revealed that highly oriented MoS2 lamellae restricted the oxidation to
the first few top layers, which led to a shorter run-in period compared to amorphous MoS2 , where the
deeper penetration of oxygen into the surface resulted in a longer run-in period (Figure 6b,d) [124].
Therefore, deposition techniques that result in a lower density of edge sites or highly oriented lamellae
of MoS2 can reduce the possibility of oxidation, thereby minimizing the degradation of tribological
performance under ambient conditions.
Lubricants 2019, 7, 57 14 of 35
Lubricants 2019, 7, x FOR PEER REVIEW 15 of 36

FigureFigure 6. The
6. The effect
effect of microstructureon
of microstructure onthe
thetribological
tribological performance
performanceofof MoS
MoS2 coatings as illustrated
2 coatings as illustrated
by thebyfriction
the friction coefficient
coefficient as a as a function
function of number
of number of cycles
of cycles for for ordered
ordered (a,b)
(a,b) andand amorphous(c,d)
amorphous (c,d)MoS
2
MoS2 films with different exposure times to atomic oxygen (AO) and O2 at different temperatures.
films with different exposure times to atomic oxygen (AO) and O2 at different temperatures. The
The lighter color in each plot represents the as-deposited coating performance. Adapted with
lighter color in each plot represents the as-deposited coating performance. Adapted with permission
permission from [124], copyright 2017 American Chemical Society.
from [124], copyright 2017 American Chemical Society.
Atomic oxygen (AO) is an abundant species (with a high flux density on the order of 1013–1015
Atomic oxygen (AO) is an abundant species (with a high flux density on the order of 1013 –1015
−2·s−1 and kinetic energy ∼5 eV) that acts on exposed surfaces of devices and components
atoms·cm
−2 −1
atoms·cmemployed ·s inand
spacekinetic energyand
applications, ∼5 eV) that acts
can cause on exposed
deterioration surfacesproperties
of material of devices andThere
[125]. components
has
employed in spaceresearch
been extensive applications,
on the and
effectcan cause
of AO on deterioration
the tribological of material properties
performance [125]. There
of MoS2 lubricants (see, has
been e.g.,
extensive researchHowever,
[122,125–129]). on the effect
thereof AO
are someon discrepancies
the tribological performance
in the of MoS
reported results: lubricants
for2instance, no (see,
e.g., [122,125–129]). However,
change in the tribological there are
properties some
of MoS discrepancies
2 after AO exposure inwas
thereported
reportedbyresults: for instance,
[128]; whereas most no
change other studies
in the reported properties
tribological high initial of
friction
MoS2due afterto AO
the limited
exposure depth
wasofreported
oxidation, byand
[128];S loss on themost
whereas
MoS coating surface [125–127,129]. Moreover, Wang et al. observed an overall
other studies reported high initial friction due to the limited depth of oxidation, and S loss on the MoS2
2 higher mean friction
coating for surface
a pure [125–127,129].
MoS2 sample with AO exposure
Moreover, Wang as wellobserved
et al. as a direct correlation
an overall between
higher meanthe wear- for a
friction
volume/friction and the AO exposure time [122]. The atomic oxygen flux density during sliding has
pure MoS2 sample with AO exposure as well as a direct correlation between the wear-volume/friction
also been shown to inversely affect the life of the coating [127]. The discrepancies in these results
and the AO exposure time [122]. The atomic oxygen flux density during sliding has also been shown
might stem from differences in experimental conditions such as atomic oxygen beam energy (thermal
to inversely
to keV), affect
fluence the(i.e.,
lifeintensity,
of the coating
1012–1024[127]. The 2discrepancies
atoms/cm in theseand/or
), sample preparation results might stem
tribological testfrom
differences in experimental
conditions [130]. conditions such as atomic oxygen beam energy (thermal to keV), fluence
(i.e., intensity, 10 12 –1024 atoms/cm2 ), sample preparation and/or tribological test conditions [130].
The effect of a humid environment, i.e., water vapor, on the friction and wear properties of MoS2
The effectcoatings
lubricant of a humid environment,
has been extensivelyi.e., water
studied vapor,
since the on the friction
mid-20th century and wear properties of MoS2
[12,103,106,107,109,131].
Generally,
lubricant the presence
coatings has been ofextensively
water molecules in thesince
studied environment (e.g., while
the mid-20th storing
century MoS2 under humid
[12,103,106,107,109,131].
conditions)
Generally, leads to an of
the presence increase
waterinmolecules
sliding friction
in and
the wear rate regardless
environment (e.g.,ofwhile
the MoS 2 film deposition
storing MoS2 under
technique employed [13,93,105,132,133]. Despite general agreement
humid conditions) leads to an increase in sliding friction and wear rate regardless of the MoS in the literature about the effect film
2
of water on the tribological behavior of MoS2, there are discrepancies regarding the governing
deposition technique employed [13,93,105,132,133]. Despite general agreement in the literature about
mechanism associated with this phenomenon. Common hypotheses for the increase in friction in
the effect of water on the tribological behavior of MoS2 , there are discrepancies regarding the governing
humid environments include:
mechanism associated with this phenomenon. Common hypotheses for the increase in friction in
• Water-driven oxidation of MoS2 edge sites [104–107,132];
humid environments include:
• Physisorption of water molecules at the surface which deteriorates the tribological behavior of
• Water-driven oxidationofof
MoS2 via disruption MoS
the edge of
easy2 shear sites [104–107,132];
lamellae [131,133–137], adhesion enhancement [138,139],
• Physisorption of waterbetween
hydrogen bonding molecules
basalatplanes
the surface
of MoSwhich deteriorates
2 [140,141] the tribological
and restriction behavior
of the growth and of
reorientation of the tribofilm [123].
MoS2 via disruption of the easy shear of lamellae [131,133–137], adhesion enhancement [138,139],
hydrogen bonding
For many years, between
oxidation basal
of MoSplanes
2 at edgeofsites
MoSwas 2 [140,141] and
thought to be restriction
the mechanismof the growth and
responsible
reorientation
for increasing offriction
the tribofilm
and wear [123].
rate of MoS2 under humid environments [104–107,132]. This
hypothesis was mainly tested in the presence of both water and oxygen species and an enhancement
For many years, oxidation of MoS2 at edge sites was thought to be the mechanism responsible for
increasing friction and wear rate of MoS2 under humid environments [104–107,132]. This hypothesis
was mainly tested in the presence of both water and oxygen species and an enhancement in oxide
Lubricants 2019, 7, 57 15 of 35

formation (and subsequent sulfur loss at the surface) was observed as the relative humidity (i.e.,
partial pressure of water) increased. As mentioned before, oxygen alone can oxidize the MoS2 film, so
the important question about the effective and distinctive role of water in oxide formation remained
unanswered in these studies. Recent experiments [109,117,131,133], and simulations [136] decoupled
the role of water and oxygen in the tribological behavior of MoS2 in humid environments. It was
found that water did not promote MoS2 oxidation at room temperature. This statement was supported
by energy-dispersive X-ray spectroscopy (EDS) analysis in which no oxygen Kα was detected on
the worn surface of lubricant films in humid nitrogen environment; i.e., water did not cause the
degree of oxidation necessary for detection in this test [131]. This finding is in agreement with Raman
spectroscopy results of Windom et al. in which a humid environment had little effect on oxidation
compared to dry air or O2 environments [117]. Moreover, increasing the temperature to values between
room temperature and the transition temperature for oxidation greatly improved the tribological
properties of the coating [131,133]. This evidence indicates that adsorption/desorption of water is a
reversible process, i.e., physisorption rather than chemisorption. Furthermore, ab initio MD simulations
modeling the interaction of water with MoS2 bilayers showed that intercalated water molecules inhibit
the sliding motion of both regular and defective layers considerably and that the sliding distance
and velocity after a given shear stress are reduced by increasing amounts of water molecules at the
interface, consistent with viscous friction behavior [136]. In a recent study, Lee et al. [137] attributed
friction enhancement in the presence of intercalated water to the enhancement of phononic energy
dissipation at the MoS2 -water interface. It has also been suggested that liquid water could be formed
by capillary condensation of vapor in the defects of the MoS2 crystal structure and that water could
then inhibit the easy shear between basal planes [138]; however, no direct observation of adhesion
enhancement has yet been reported.
A new interpretation on the role of water in the tribological behavior of MoS2 was recently
proposed by Curry et al. [123]. It was observed that the run-in coefficient of friction for highly-oriented
MoS2 remains the same under dry and humid environments, whereas the run-in behavior is highly
environment-dependent in the case of amorphous films. Consequently, it was suggested that water
restricted the formation and growth of the shear-induced, highly ordered tribofilms instead of
deteriorating the shear strength of existing highly ordered tribofilms. This hypothesis needs further
investigation for confirmation.
Recent computational studies [136,142–144] of the energetics and mechanisms of water adsorption
and dissociation on MoS2 films showed that oxidation is much less likely than the simple adsorption
of water molecules at edge sites. Additionally, the most favorable locations for the adsorption
of water molecules were determined to be Mo edge sites. However, at room temperature, water
molecules could dissociate to O and OH that bind to all available edge sites on MoS2 (i.e., not just
Mo) [143]. The higher reactivity of the edges in MoS2 films emphasizes the potential role of the
microstructure in the tribological response of MoS2 under ambient conditions; the presence of highly
ordered structures can significantly improve the tribological behavior of MoS2 coatings in humid
environments [48,123,145–147]. To tailor the microstructure for improving the lubricative properties of
MoS2 under ambient conditions, Chhowalla et al. [148] followed a different approach and generated
a thin film of lubricant made of hollow fullerene-like MoS2 clusters (“onions”) using the localized
arc discharge method. Ultra-low friction and wear were observed in a humid environment and
attributed to the presence of curved S–Mo–S planes that prevented oxidation and preserved the layered
structure [148].
Overall, the presence of any environmental contaminant degrades the excellent tribological
properties of MoS2 observed in vacuum. Below the transition temperature for oxidation, water
adsorption disrupts the easy-shear properties of MoS2 , whereby oxygen plays only a marginal role
in degrading its tribological properties. The adsorption of water is thermodynamically favored, and
water diffusion in the bulk has a direct correlation with R.H. and exposure time. As the temperature
increases, water species desorb and an improvement in the tribological properties of MoS2 can be
Lubricants 2019, 7, 57 16 of 35

observed. As the temperature approaches the transition temperature, oxygen-driven, surface-limited

oxidation becomes significant and thus, oxidation deteriorates the excellent lubricity of MoS
Lubricants 2019, 7, x FOR PEER REVIEW 2 at
17 of 36
high
temperatures in ambient conditions [131].
oxidation
At becomestemperatures
high service significant and (i.e.,thus, above
oxidationthedeteriorates
transitionthe excellent lubricity
temperature), of MoS
friction 2 at high with
increases
temperatures
increasing in ambient
temperature; underconditions
ambient [131].
conditions this is due to increasing oxidation rates, whereas
the thermal At high service temperatures
dissociation rates of MoS (i.e.,rapidly
above the transition
increase temperature),
in inert friction increases
gas or vacuum environments with at
2
increasing temperature; ◦ under ambient conditions this is due to increasing oxidation rates, whereas
temperatures above 500 C [109,118,149,150]. Within this context, the maximum temperature at which
the thermal dissociation rates of MoS2 rapidly increase in inert gas or vacuum environments at
MoS2 provides effective lubrication is highly dependent on (i) the operating environment, e.g., the
temperatures above 500 °C [109,118,149,150]. Within this context, the maximum temperature at which
presence or absence of vacuum and the humidity level, and (ii) the microstructural properties of the
MoS2 provides effective lubrication is highly dependent on (i) the operating environment, e.g., the
MoS2presence
coating,orincluding
absence ofitsvacuumcrystaland structure, density,
the humidity andand
level, surface
(ii) theroughness.
microstructuralFor instance,
propertiesin ofvacuum,
the
the maximum operating temperature of burnished MoS ◦
MoS2 coating, including its crystal structure, density, and 2 is in theroughness.
surface range of 600–700
For instance,C because
in vacuum, thermal
dissociation of MoS
the maximum 2 around
operating these
temperaturetemperatures
of burnished deteriorates
MoS 2 is in its
the lubricative
range of properties
600–700 °C because[149]. However,
thermal
dissociation
mechanically of MoS2MoS
deposited around these under
2 coatings temperatures
ambientdeteriorates
conditionsits lubricative
could properties [149].
have a maximum operation
However, ◦
mechanically deposited MoS coatings under ambient
temperature of 400 C due to the rapid oxidation of MoS2 [115,150]. The main challenge therefore is to
2 conditions could have a maximum
developoperation
MoS2 temperature
based coatings of 400 °C due
which cantobethe rapid
used oxidation
over a wideofrange MoS2of [115,150].
operating Thetemperatures.
main challenge
therefore is to develop MoS2 based coatings which can be used over a wide range of operating
While the influence of temperature on the tribological properties of MoS2 under ambient
temperatures.
conditions is related to effects associated with the presence of oxygen and water vapor [109,118,149],
While the influence of temperature on the tribological properties of MoS2 under ambient
temperature
conditions hasis also
related been shownassociated
to effects to affect with friction and wear
the presence ofunder
oxygenvacuum and water conditions [151–154] and
vapor [109,118,149],
dry nitrogen
temperature environments
has also been[155–157].
shown to affect However,
friction there
and wear is disagreement
under vacuum in these reports
conditions [151–154] forand
the low
temperature tribological behavior of MoS (from the cryogenic regime to around −150 ◦ C). Some
dry nitrogen environments [155–157]. However, 2 there is disagreement in these reports for the low
studies [152,156] tribological
temperature reported monotonic
behavior ofincreases
MoS2 (from in the
friction coefficient
cryogenic regimewith decreasing
to around −150 °C). temperature,
Some
whilestudies [152,156][151,153,155,157]
other studies reported monotonic increasesthat
suggested in friction
decreasing coefficient with decreasing
the temperature below temperature,
a certain level
does while
not leadothertostudies
increasing[151,153,155,157] suggested (Figure
friction coefficients that decreasing the temperature
7). At moderate below a certain
temperatures (up to level
around
◦ does not lead to increasing friction coefficients (Figure 7). At moderate
200 C), the friction, in a thermally activated process, monotonically decreases as temperature increases. temperatures (up to around
200 °C), the friction, in a thermally activated process, monotonically decreases as temperature
Wear rate in this temperature range has been reported to increase as temperature increases, such
increases. Wear rate in this temperature range has been reported to increase as temperature increases,
that the wear rate of an MoS2 coating doubled as temperature increased from −100 to 100 ◦ C [151].
such that the wear rate of an MoS2 coating doubled as temperature increased from −100 to 100 °C
Curry[151].
et al.Curry
[154]etrecently
al. [154] developed
recently developed a predictive modelmodel
a predictive to correlate
to correlatethe the
macroscale
macroscale interfacial
interfacialshear
strength of MoS
shear strength 2 to temperature, based on the temperature-dependent
of MoS2 to temperature, based on the temperature-dependent probabilities for probabilities for commensurate
or incommensurate
commensurate or sliding to occur, taking
incommensurate slidinginto account
to occur, takingthe into
corresponding
account the energy barriersenergy
corresponding to sliding.
One hypothesis that has
barriers to sliding. One emerged
hypothesis fromthat these studies is
has emerged that
from the studies
these thermally-activated friction behavior is
is that the thermally-activated
limitedfriction behaviorwhere
to situations is limited to situations
negligible wear takeswhereplace,
negligible
and thatwearthe takes place, and
transition fromthat the transition
thermally activated
from thermally activated friction to
friction to athermal friction is a direct result of wear. athermal friction is a direct result of wear.

FigureFigure
7. (a)7.Friction
(a) Friction force
force obtained
obtained from
from AFM
AFM lateralforce
lateral forcemeasurements
measurements at
at different
differenttemperatures
temperatures for
for a Si 3N4 tip sliding over MoS2. (Inset) Friction-load dependence of this system at T = 200 K; (b)
a Si3 N4 tip sliding over MoS2 . (Inset) Friction-load dependence of this system at T = 200 K; (b) Friction
Friction coefficients obtained from friction-load plots as a function of temperature. (Inset) Adhesion
coefficients obtained from friction-load plots as a function of temperature. (Inset) Adhesion forces
forces measured at each temperature range. Reprinted with permission from [153], copyright 2009 by
measured at each temperature range. Reprinted with permission from [153], copyright 2009 by the
the American Physical Society.
American Physical Society.
Research efforts aimed at achieving MoS2 solid lubricant coatings that are robust with respect to
Research efforts aimed at achieving MoS2 solid lubricant coatings that are robust with respect
changes in environment and temperature have primarily used two approaches: (i) changing the
to changes in environment and temperature have primarily used two approaches: (i) changing the
Lubricants 2019, 7, 57 17 of 35

method and parameters of deposition and (ii) adding dopants. First, microstructural properties
can be improved by varying the deposition method (such as by using N2 -spray-deposition [123],
unbalanced magnetron sputtering [145] or ion-beam-assisted deposition [158]) or parameters (such
as lowering the sputter gas pressure [159]) during film preparation to obtain dense films with highly
oriented basal planes parallel to the substrate and with the lowest possible density of defects and edge
sites. As briefly mentioned above, this approach can improve the environmental resistance of MoS2
lubricants [123,145–147]. Second, by addition of a small amount of other materials such as metals
and inorganic sulfides/oxides, the coating density (and consequently, internal stress), hardness and
oxidation resistance can be improved. The effect of dopants on the tribological properties of MoS2
lubricants is discussed in more detail in Section 6.
To extend the operating range of MoS2 coatings, adaptive composite coatings have been widely
studied. The composite coating improves lubrication not only by the presence of the coating
constituents but also by the lubricious products of chemical or physical reactions that happen during
sliding. While a comprehensive coverage of the utilization of MoS2 in composite coatings is not
within the scope of this review article, several notable examples will be mentioned here due to their
relevance for temperature dependence work. Examples of such adaptive composite coatings include
PbO/MoS2 [55,160], YSZ–Ag–Mo–MoS2 [161], Mo2 N/MoS2 /Ag [162] and Ag/MoS2 /graphite [163]
which extend effective lubrication capabilities over a wide temperature range by combining the
lubricity of MoS2 at lower temperatures and the creation of oxides with easy shear properties at high
temperatures [164–166]. However, the chemical reactions are not reversible and the oxides do not
provide lubrication at low temperatures, so the ability to withstand thermal cycling is a challenge [167].
One approach is to establish barrier layers to protect some MoS2 from oxidation [168]. In a different
approach to extend the effective lubrication temperature range, Zhang et al. [169] achieved a low
friction coefficient (∼0.03) and low wear rate (∼10−13 mm3 /N·mm) at 300 ◦ C using carbon nanotube
(CNT)/MoS2 composite coatings. These improvements in tribological properties were attributed to
an enhancement of mechanical strength due to the high load-bearing capacity of CNTs. Several
studies [170,171] showed that diamond-like carbon (DLC) can also be added to the adaptive coating in
order to enhance its service temperature range. The DLC phase in these coatings increased hardness
and provided a source of carbon for surface graphitization effective for humid environment lubrication.
For a detailed description of adaptive coatings designed to improve the temperature range for effective
lubrication by MoS2 , readers are referred to [164,172].

6. Structure and Tribological Properties of Doped MoS2

6.1. Structure of Doped MoS2

While most studies of structural characterization on doped MoS2 have focused on synthetic
approaches and the effects of doping on electronic structure and catalysis, the obtained results on
atomic-scale structure can also be beneficial for the use of doped MoS2 as a solid lubricant. Here we
review the available literature with atomistic characterization of the structures of doped MoS2 , with a
focus on bulk rather than monolayers. Experimental characterization of a heterogeneous structure
(unlike a single crystal) is quite challenging and, therefore, DFT calculations have played a key role in
elucidating structures.
Dopants in MoS2 can be incorporated in several possible locations. Substitution can occur at
either the Mo or S site. Atoms can be added (intercalated) between the MoS2 layers. They can also be
adsorbed at a surface, as adatoms on an MoS2 sheet (basal plane) or on an edge, which is particularly
likely for few-layer MoS2 or nanosheets. In principle, there could be interstitials within a MoS2
layer, in the sites within an Mo plane, but there is very limited space and such a structure does not
seem to be observed. Adatoms can occur in several high-symmetry sites such as atop Mo, atop S,
bridging an Mo-S bond, or in the center of a hexagonal hollow [173]. If an atom is intercalated between
two layers in the 2H polytype, these become just two high-symmetry positions: tetrahedrally- or
 can be formed.
Most doping studies of MoS2 have used transition metals, which are chemically similar to Mo.
DFT calculations for monolayer MoS2 found that Fe, Mn, W, Cr, V, and Ti dopants substituting for
Mo maintain its six-fold coordination, whereas Zn, Au, Ag, Cu, Pt, Pd, Ni, and Co break symmetry
and adopt four-fold coordination [178]. A DFT study of Mo substitution on the basal plane surface of
Lubricants bulk 7,found
the 2019, 57 18 of 35
five-fold coordination for Co, Ni, and Cu, and a six-fold coordination but distorted
geometry for Fe; all had shorter M–S bond lengths. Substitution at the edge rather the basal plane
was energetically favored [179]. By contrast to the DFT study, experimental results on Zn doping of
octahedrally-coordinated [174]. These possible dopant locations in bulk 2H MoS2 are depicted in
MoS2 nanosheets showed little change in Raman or XRD, and were interpreted as Mo substitution
Figure 8.
without structural distortion [184].

FigureFigure 8. Possibledoping
8. Possible doping sites
sites in
in 2H
2HMoS
MoS2: substitution at theatS the
2 : substitution site,Ssubstitution at the Mo
site, substitution atsite,
the Mo
octahedral intercalation,
site, octahedral andand
intercalation, tetrahedral intercalation.
tetrahedral Unsubstituted
intercalation. Mo and S Mo
Unsubstituted are gray
andand yellow,
S are gray and
respectively.
yellow, respectively.

Re can occur
The favorable naturally
dopants andintheir
MoS2locations
. Re substitution
can beofunderstood
Mo has a low calculated
with several formation energy[175].
considerations
[27], and it can drive structural 4+
changes to2– 1T or 3R. ReS2 has a similar structure
+ to MoS2 although it
Since MoS2 formally involves Mo and S ions, atoms that can adopt a 4 oxidation state naturally
does have Re-Re bonds in plane [175]; Re doping by a diffusion process resulted in a 1:100 Re:Mo
fit the Mo site, while atoms that can adopt a 2− oxidation state fit the S site. Intercalated atoms are
ratio. No Raman changes were0observed, and in particular no sign of ReS2 formation. TEM showed
expected
Re intoMobe neutral.
sites, andThe atomincrease
a small s ionic radius
in the and its compatibility
in-plane lattice spacing,with the scanning
while Mo or S radii,
tunnelingwhether
the atom
microscopy (STM) suggested Mo substitution within grains and intercalation at grain boundariesatom
has similar bond length with Mo or S when compared to those in MoS 2 , and whether the
forms[185].
a crystal with
Another STMMostudy
or S of similar
also showedstructure to MoS2by
Mo substitution areRekey points.
[186]. When
Pt doping has these
beenare all similar
studied for to
MoS2catalysis.
, alloyingExtended
in varying proportions
X-ray may
absorption be structure
fine possible, (EXAFS)
as is the case
showedfor Mo Wx S2 , MoS
Pt–S1-xbonds, 2(1-x) Se
indicated 2x , and
Mo
Mo1-xsubstitution, andhave
Nbx S2 , which showed no signsmixing
favorable of Pt–Pt energies
bonds, indicating
and canthat Pt clusters
show were notdisorder
substitutional present [178].
[174,176].
The chemical potentials of Mo, S, and the dopant under synthesis conditions will control which dopant
location is favored: for example, S-rich conditions favor Mo substitution [177]. Doping can perturb
the local structure (including symmetry breaking and Jahn-Teller distortions) [178,179], alter lattice
parameters, or even favor an overall change in crystal structure to a different polytype: Li intercalation
causes a change from 2H to 1T [180], and Nb substitution of Mo favors 3R over 2H [181]. Dopants can
affect the growth process [182] and the morphology of the resulting crystals or nanostructures, via
kinetic or thermodynamic effects [175]. Dopants can be well dispersed or may tend to cluster [177],
and in some cases may segregate into competing phases [182,183]. Theoretical studies are complicated
by the non-equilibrium conditions in many synthesis approaches, meaning that not only lowest energy
structures but also other thermodynamically metastable phases can be formed.
Most doping studies of MoS2 have used transition metals, which are chemically similar to Mo.
DFT calculations for monolayer MoS2 found that Fe, Mn, W, Cr, V, and Ti dopants substituting for
Mo maintain its six-fold coordination, whereas Zn, Au, Ag, Cu, Pt, Pd, Ni, and Co break symmetry
and adopt four-fold coordination [178]. A DFT study of Mo substitution on the basal plane surface of
the bulk found five-fold coordination for Co, Ni, and Cu, and a six-fold coordination but distorted
geometry for Fe; all had shorter M–S bond lengths. Substitution at the edge rather the basal plane was
energetically favored [179]. By contrast to the DFT study, experimental results on Zn doping of MoS2
nanosheets showed little change in Raman or XRD, and were interpreted as Mo substitution without
structural distortion [184].
Re can occur naturally in MoS2 . Re substitution of Mo has a low calculated formation energy [27],
and it can drive structural changes to 1T or 3R. ReS2 has a similar structure to MoS2 although it does
have Re-Re bonds in plane [175]; Re doping by a diffusion process resulted in a 1:100 Re:Mo ratio. No
Raman changes were observed, and in particular no sign of ReS2 formation. TEM showed Re in Mo
sites, and a small increase in the in-plane lattice spacing, while scanning tunneling microscopy (STM)
Lubricants 2019, 7, 57 19 of 35

suggested Mo substitution within grains and intercalation at grain boundaries [185]. Another STM
study also showed Mo substitution by Re [186]. Pt doping has been studied for catalysis. Extended
X-ray absorption fine structure (EXAFS) showed Pt–S bonds, indicated Mo substitution, and showed
no signs of Pt–Pt bonds, indicating that Pt clusters were not present [178].
Nb doping has been extensively studied since it causes little change in the bonding or electronic
structure, which
Lubricants 2019, is
7, xideal
FOR PEERfor electronic
REVIEW doping [177,181]. DFT calculations showed alloying20isofpossible 36
with Nb substituting for Mo up to 25% [174]. Nb has the same oxidation state and a similar ionic
radius to Nb Mo,doping
and the hasNbS been2 extensively
phase exists, studied
albeitsince
withit causes little change
a different in the
stacking. DFT bonding
showsorthe electronic
octahedral
structure, which is ideal for electronic doping [177,181]. DFT calculations
intercalated site is favored over tetrahedral, but Mo substitution is much more favored. There showed alloying is possible
is a local
with Nb substituting for Mo up to 25% [174]. Nb has the same oxidation state and a similar ionic
distortion toward the NbS2 bond lengths [174]. Pairing of Nb dopants in the monolayer is favored
radius to Mo, and the NbS2 phase exists, albeit with a different stacking. DFT shows the octahedral
by 0.16 eV [177] but only by 0.01 eV in bulk [174]. TEM showed the lattice spacing is preserved and
intercalated site is favored over tetrahedral, but Mo substitution is much more favored. There is a
the Raman spectrumtoward
local distortion showed theonly
NbSsubtle changes. Energy-filtered electron transmission microscopy
2 bond lengths [174]. Pairing of Nb dopants in the monolayer is
spectrum imaging (EFTEM-SI) showed
favored by 0.16 eV [177] but only by 0.01 eV well dispersed Nb, and
in bulk [174]. TEMEXAFS
showedshowed thespacing
the lattice same atomic
is
environment
preserved forand
Nb and the Mo Raman [187].spectrum
Interestingly,
showed Nb only
doping can also
subtle induce
changes. a transformation
Energy-filtered from the
electron
2H structure
transmissionto 3Rmicroscopy
[181]. spectrum imaging (EFTEM-SI) showed well dispersed Nb, and EXAFS
Ni doping has been investigatedfor
showed the same atomic environment forNbtribology
and Mo [187].andInterestingly,
catalysis. Nb doping cancan
Sputtering alsoincorporate
induce
a transformation from the 2H structure to 3R [181].
5%–7% concentrations, and it increases the size of acicular (needle-shaped) crystallites [85]. Low
Ni doping
concentrations of Nihas been investigated
increase MoS2 crystal forsize
tribology and catalysis.
in hydrothermal Sputtering
synthesis, canchange
and incorporate 5%–7%
crystallographic
concentrations, and it increases the size of acicular (needle-shaped) crystallites [85]. Low
orientations. XPS showed the presence of Ni0 and Ni2+ , consistent with intercalation and substitution.
concentrations of Ni increase MoS2 crystal size in hydrothermal synthesis, and change
High concentrations of Ni cause formation of Ni sulfides0 instead; Ni3 S4 was seen in XRD and
crystallographic orientations. XPS showed the presence of Ni and Ni2+, consistent with intercalation
0 s calculated
Raman and[182], which High
substitution. is theconcentrations
most stable of NiNix Sycause
phase according
formation of Nitosulfides
the Materials
instead; Ni Project
3S4 was seen in
phaseXRDdiagram [22,188].
and Raman Another
[182], whichXPS study
is the mostsuggested
stable NixNi in nanoclusters
Sy phase according isto neutral but easily
the Materials oxidizes
Project′s
to Ni2+ [28].
in aircalculated Mo substitution is suggested by an XRD/AFM study
phase diagram [22,188]. Another XPS study suggested Ni in nanoclusters is neutral but of 10% doping showing
the same
easilystructure
oxidizes in asairundoped
to Ni2+ [28].material [189]. Cois doping
Mo substitution suggested is by
also
an common
XRD/AFMfor catalysis.
study Co and Ni
of 10% doping
in MoSshowing the same structure
2 nanoclusters occur asasMo undoped materialnear
substituents [189].the
Coedges,
dopingchanging
is also common
themfor catalysis.
from Co to
triangular
and Ni
truncated in MoSwhich
shapes, 2 nanoclusters
is seenoccur
by STMas Mo substituents
(Figure 9) andnear the edges,
predicted by changing
DFT. EXAFS themindicates
from triangular
Co and Ni
have to truncated shapes,
approximately fivewhich
bonds is seen
to S by STM (Figure
neighbors, 9) and predicted
consistent with Mobysites DFT.near
EXAFS an indicates
edge (or Co and
a distorted
Ni have approximately five bonds to S neighbors, consistent with Mo sites near an edge (or a distorted
geometry) [190]. Evidence from EXAFS, STEM (scanning transmission electron microscopy) and DFT
geometry) [190]. Evidence from EXAFS, STEM (scanning transmission electron microscopy) and DFT
for monolayer MoS2 has shown Co not only in Mo sites but also S sites, and as adatoms in various
for monolayer MoS2 has shown Co not only in Mo sites but also S sites, and as adatoms in various
positions [173].
positions [173].

Figure
Figure 9. (a)9.Atom-resolved
(a) Atom-resolved STM
STM imageofofaaCo-doped
image Co-doped MoS
MoS2 2nanosheet
nanosheetonon
an an
AuAusurface, showing
surface, showing
substitution of Mo atoms near edges; (b) Ball model. S: yellow, Mo: blue, Co: red. Reprinted from
substitution of Mo atoms near edges; (b) Ball model. S: yellow, Mo: blue, Co: red. Reprinted from [190]
[190] with permission from Elsevier.
with permission from Elsevier.
Doping with Ti and Zr has been found to distort the structure and reduce crystallinity at high
Doping with Ti and Zr has been found to distort the structure and reduce crystallinity at high
doping levels, related to the octahedral coordination in TiS2 and ZrS2. The out-of-plane lattice
doping levels, related to the octahedral coordination in TiS and ZrS . The out-of-plane lattice
parameter was not found to change much in XRD. V intercalates2and shows2expanded layers in XRD,
parameter was in
remaining notthe
found to change
2H polytype. Crmuch
has 2+inand
XRD.
3+ V intercalates
oxidation states,and shows
unlike expanded
4+ for Mo, andlayers in XRD,
therefore
remaining
causesin the 2H polytype.
disordering Cr has enhances
[175]. Cr doping 2+ and 3+ theoxidation states, unlike
MoS2 longitudinal 4+band
acoustic for Mo, and
in the therefore
Raman
causes disordering
spectrum, with an[175]. Cr doping
intensity enhances
linear with dopingthe MoS
level. longitudinal
Energy-dispersive
2 acoustic
X-ray band in
spectroscopy the Raman
(EDX)
showed dispersal of Cr throughout flakes, and the elastic modulus was found to be increased [191].
Group VI elements can straightforwardly substitute for S. MoSe2(1-x)S2x alloys are reported to be
favorable [176]. MoS2(1-x)O2x (based on MoO4) has been observed by EXAFS [183] and found to have
decreased crystallinity and an expanded interlayer spacing [192]. MoSxO3-x (based on MoO3) has been
Lubricants 2019, 7, 57 20 of 35

spectrum, with an intensity linear with doping level. Energy-dispersive X-ray spectroscopy (EDX)
showed dispersal of Cr throughout flakes, and the elastic modulus was found to be increased [191].
Group VI elements can straightforwardly substitute for S. MoSe2(1-x) S2x alloys are reported to
be favorable [176]. MoS2(1-x) O2x (based on MoO4 ) has been observed by EXAFS [183] and found to
have decreased crystallinity and an expanded interlayer spacing [192]. MoSx O3-x (based on MoO3 ) has
been identified through Raman and XPS [193]. Se and Te substitution at 25% causes small systematic
changes in lattice parameter. AFM showed the same surface structure for Se, but Te was found to result
in surface protrusions [189]. Halogens (F, Cl, Br, I) substituting on the S site have been calculated to
have large formation energies, but perhaps substitution could occur by filling S vacancies [177], as
suggested by experiments [194]. N doping at the S site has been suggested by XPS, with DFT showing
N adopting a “groove” position lower than the S atom plane [195]. Phosphorus is believed to substitute
for S, as shown in a laser-doping study of the monolayer, in which sulfur vacancies are created as
a first step. The long-term stability of photoluminescence suggested substitution by P rather than
surface adsorption as adatoms [196]. H or alkali (Li, K, Cs) atoms can adsorb on MoS2 and donate
electrons, preferring a location atop the Mo site [177]. Li can also intercalate, driving 2H to 1T crystal
structure transformations, and large changes in the Raman spectrum; this process can be used in Li-ion
batteries [180].

6.2. Tribological Properties of Doped MoS2

Dopants have been used to improve the tribological properties of MoS2 coatings for several
decades [175]. As discussed in Section 6.1, dopant atoms can exist in layered structures through
substitution of atoms in the lattice, at interstitial sites between atoms in the lattice, intercalated between
layers, or as a separate phase dispersed in the material. Which of these is observed depends on the
dopant and its concentration, as well as the deposition process used to create the coating. Doped
coatings are produced using various deposition methods. Sputter deposition, also called sputtering,
was one of the earliest techniques and is still commonly used. However, also applied for doped MoS2
coatings are unbalanced magnetron sputtering, ion beam deposition, and pulsed laser deposition [15].
Dopants that have been studied and shown to improve tribological properties of MoS2 are Ni, Cr, Ti,
Au, Zr, and Sb2 O3 . Doped MoS2 coatings have been shown to exhibit better tribological properties
(i.e., friction, wear and life) than undoped MoS2 in vacuum, as well as exhibit superior resistance to
oxidation which improves performance and storability in air [15].
Understanding the mechanisms by which dopants improve the tribological and oxidation
properties of MoS2 is still a topic of active research. In terms of oxidation resistance, multiple
mechanisms have been proposed. First, dopants are thought to affect the growth of MoS2 crystallites
which reduces MoS2 phase size and in turn increases density [15]. Higher density can improve
oxidation resistance by reducing crystalline breakage [197], as well as decreasing the number of edge
sites available to oxidize [15]. Dopants are also proposed to passivate edge sites so that they are less
reactive with available oxygen [198]. Lastly, in cases where dopants exist as a separate phase, it has
been proposed that the dopant atoms bond with oxygen to form an oxide [199].
The beneficial effects of dopants on friction, wear and coating life have also been explained via
multiple mechanisms. However, the most widely cited mechanism is increased hardness [65,67,175,200–
203]. It has been proposed that hardness increases as a result of distortion of the MoS2 crystal structure
in doped films [65,67]. Hardness directly benefits wear, which is critical for coating life (or endurance)
in many applications, including space missions where coatings must function for many years without
replacement. Some papers that report improved hardness also observe that dopants can increase the
elastic modulus of the coating [201–203]. Hardness has also been associated with increased density
(sometimes referred to as reduced porosity) that contributes to improved friction and wear [204,205].
However, increased hardness is not the only mechanism available, and it has been shown that some
dopants decrease hardness yet improve performance [198]. For some dopants, the primary mechanism
is proposed to be the presence of the dopant as a separate nanoscale phase which imparts beneficial
Lubricants 2019, 7, 57 21 of 35

properties related to the transfer film [200,206,207]. In practice, the mechanism or mechanisms by
which a dopant improves coating performance depends on the dopant, its concentration and, to some
degree, conditions during coating deposition and operation. For some of the mostly commonly studied
dopants, these effects are discussed in more detail below, grouped by proposed mechanism.
Of the dopants believed to improve tribological performance through hardening, Ti has been
the most widely studied [65,85,157,198,201,208,209]. It has been proposed that the Ti atoms are either
intercalated between MoS2 layers [67] or substituted with Mo based on observation of a lack of change
in crystal c-axis after doping [210]. Ti atoms have been found to be uniformly distributed in the MoS2
matrix with no Ti-rich clusters or precipitates present [211]. Measurements of 16% Ti coatings showed
that the films are slightly sub-stoichiometric in sulfur and amorphous [209]. Ti-doped coatings have
been reported to have a columnar platelet structure, with higher concentrations of Ti corresponding
to increasing density [212]. Ti has been found to increase coating hardness, but only up to a limiting
concentration, after which additional Ti has a detrimental effect [67,212]. Tribological properties also
improve with the amount of Ti in the coating, up to a limiting value that has been reported to be
18% [67]. Ti improves oxidation resistance, as verified by measuring the same friction with 10.8% Ti
across a range of humidities [212]. Lastly, it was found that Ti-doped MoS2 performance depends on
the counterface material, with ZrO2 being best among brass, GCr15 steel, WC and ZrO2 [203].
The hardening mechanism has also been used to explain the beneficial effects of Cr [65,85,198] [208],
Zn [65,200], and Ni [85,157,197] dopants to improve friction and wear. The optimum concentration
of Cr was found to be 16.6% for hardness and 10% for friction and wear [208]. Zr-doped coatings
were found to consist of nanocrystalline Zr in an amorphous matrix and optimum performance was
observed at a concentration of 10% [200]. Ni has been shown to improve tribological performance
and particularly to mitigate the increase in friction with decreasing temperature that is commonly
observed with both MoS2 and other doped MoS2 coatings (see Figure 10) [157]. Ni dopants are
currently used in several space components [15] because they improve tribological performance at low
temperature [157] and are available at more reasonable cost than some of the other metallic dopant
options [85]. In general, metal dopants have been shown to increase performance up to some maximum
concentration (e.g., 11% [197]), above which the solubility limit is reached, resulting in layering and
poor tribological performance [65]. Lastly, doping with Sb2 O3 [157,197] results in a fine-grained
microstructure and a two-phase system with MoS2 crystallites dispersed in amorphous antimony
oxide [197]. The Sb2 O3 -doped coatings were found to have increased density and hardness [205] with
an optimum concentration of 35% [197].
The most commonly studied dopant that does not increase hardness is Au [198,201,204,206,207,213].
Unlike Ti, Au-doped MoS2 consists of domains of nanocrystalline Au particles dispersed in the MoS2
matrix, where the size of the particles depends on temperature [206,207]. Au dopants have been
shown to decrease hardness [198], so tribological improvement is through a different mechanism. It
has been proposed that subsurface coarsening of Au nanoparticles provides load support to allow
shear of surface MoS2 basal planes [206]. Direct comparison of MoS2 , Au and Au-doped MoS2 (at
relatively high concentrations >42%) showed the doped coating was superior to both MoS2 and Au
alone. Further, it was reported that the optimal amount of Au was dependent on contact stress, where
less Au was better at high stress and more Au was better at low stress [207,213]. To explain this
observation, it was hypothesized that, at high stress, Au provided the optimum amount of MoS2 in the
contact, while at low stress more Au limited the amount/size of MoS2 transferred, providing a thinner,
more uniform transfer film [213]. This hypothesis was consistent with the observation that sliding on
Au-doped MoS2 results in the formation of pure, crystalline, aligned MoS2 about 1 nm thick on the
coating (see Figure 11) [206,207].
 dopant options [85]. In general, metal dopants have been shown to increase performance up to some
maximum concentration (e.g., 11% [197]), above which the solubility limit is reached, resulting in
layering and poor tribological performance [65]. Lastly, doping with Sb2O3 [157,197] results in a fine-
grained microstructure and a two-phase system with MoS2 crystallites dispersed in amorphous
Lubricants 2019, 7,oxide
antimony 57 [197]. The Sb2O3-doped coatings were found to have increased density and hardness 22 of 35
[205] with an optimum concentration of 35% [197].

Lubricants 2019, 7, x FOR PEER REVIEW 23 of 36

particles dispersed in the MoS2 matrix, where the size of the particles depends on temperature
[206,207]. Au dopants have been shown to decrease hardness [198], so tribological improvement is
through a different mechanism. It has been proposed that subsurface coarsening of Au nanoparticles
provides load support to allow shear of surface MoS2 basal planes [206]. Direct comparison of MoS2,
Au and Au-doped MoS2 (at relatively high concentrations >42%) showed the doped coating was
superior to both MoS2 and Au alone. Further, it was reported that the optimal amount of Au was
dependent on contact stress, where less Au was better at high stress and more Au was better at low
stress [207,213]. To explain this observation, it was hypothesized that, at high stress, Au provided the
optimum amount of MoS2 in the contact, while at low stress more Au limited the amount/size of MoS2
transferred,
Figure providing
Average
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The most commonly studied dopant that does not increase hardness is Au
[198,201,204,206,207,213]. Unlike Ti, Au-doped MoS2 consists of domains of nanocrystalline Au

Figure 11. (a)

Figure 11.Schematic of the of
(a) Schematic contact-stress-dependent behavior
the contact-stress-dependent of Au-doped
behavior MoS2 coatings
of Au-doped supported
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2 to leveragethe
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mechanismsthat thatare available,
are available, to
to achieve even better tribological performance (particularly in terms of wear resistance). Specifically,
achieve even better tribological performance (particularly in terms of wear resistance). Specifically,
Sb2 OSb 2O3/Au doped MoS2 has been frequently studied [157,197,202,214]. For example, coatings with
3 /Au doped MoS2 has been frequently studied [157,197,202,214]. For example, coatings with good
good tribological performance consisted of 11% Sb2O3 and 7% Au [214]. Sb2O3/Au-doped MoS2 was
tribological performance consisted of 11% Sb2 O3 and 7% Au [214]. Sb2 O3 /Au-doped MoS2 was found
found to have an order of magnitude lower wear rate than Sb2O3-doped MoS2 at room temperature
[157]. This feature is particularly important for space applications for which endurance is the most
important factor, so Sb2O3/Au coatings are currently in use for some space components [15].
Several studies have compared multiple dopants. In measurements of friction and life of Ni, Fe,
Au, and Sb2O3 doped coatings, all were better than undoped MoS2 and, among the group, the best
was found to be Sb2O3/Au [197]. Another comparative study of friction and endurance that included
Lubricants 2019, 7, 57 23 of 35

to have an order of magnitude lower wear rate than Sb2 O3 -doped MoS2 at room temperature [157].
This feature is particularly important for space applications for which endurance is the most important
factor, so Sb2 O3 /Au coatings are currently in use for some space components [15].
Several studies have compared multiple dopants. In measurements of friction and life of Ni, Fe,
Au, and Sb2 O3 doped coatings, all were better than undoped MoS2 and, among the group, the best was
found to be Sb2 O3 /Au [197]. Another comparative study of friction and endurance that included Al,
Pt, Ag, W, Cr, Co, Ni, and Ti showed some dopants did not improve performance (Al, Pt, Ag, W) while
others had a positive effect (Cr, Co, Ni Ti). For those that improved performance, the optimal metal
content was found to be 5%–8% [85]. Another study of metallic dopants showed no difference between
the various dopants [65]. In a comparison between Au, Ti, Cr, and WSe2 , the lowest friction and life
were exhibited by WSe2 , followed by Au, Ti, and then Cr [198]. Another study focused on temperature
dependence measured friction and wear from −80 to 180 ◦ C for Sb2 O3 /Au, Sb2 O3 /C, Sb2 O3 , Ti, and
Ni [157]. As shown in Figure 10, they found that Sb2 O3 /Au had the lowest friction above −25 ◦ C, but
Ni had the lowest friction at −80 ◦ C. Sb2 O3 /Au exhibited the lowest wear rate at room temperature.
An inverse relationship between wear rate and the change in friction coefficient with temperature
was also observed, i.e., high room-temperature wear corresponded to smaller increase in friction with
decreasing temperature [157]. Opposite trends in friction and wear were observed in another study
as well [198]. One challenge with comparison between doped coatings is that different deposition
methods may be used for different dopants, which can affect the properties of the resultant coating.
One study isolated this parameter by comparing undoped MoS2 , Ti-doped, and Sb2 O3 /Au-doped
coatings deposited in the same way [202]. In terms of wear, MoS2 was best at 30 ◦ C and worst at
100 ◦ C, Sb2 O3 /Au was highly abrasive at 30 ◦ C but performed well at 100 ◦ C, and Ti exhibited good
tribological behavior at both temperatures [202].
In summary, dopants have been shown to consistently improve the tribological performance of
MoS2 coatings. There are many different types of dopants, but they can be generally categorized into
hard materials (Ti, Ni, Sb2 O3 ) and soft materials (Au). In terms of oxidation resistance, the possible
roles of these dopants are to densify the film (limiting the number of reactive sites available), passivate
edge sites, and sacrificially bond with oxygen. It is possible that all these mechanisms contribute to
improved oxidation resistance of doped MoS2 films. Friction, wear and life of the coatings can also be
improved through different mechanisms. However, these mechanisms are highly dependent on the
dopant and can be mutually exclusive. Hard materials densify and harden the film, providing direct
wear resistance. Soft materials appear to enable formation of thinner and more even MoS2 films on
the surface of the coating, indirectly leading to lower wear. Coatings that contain both hard and soft
materials, e.g., Sb2 O3 /Au, may take advantage of both mechanisms. However, a key observation is
that wear is often inversely related to friction, particularly friction at low temperatures. Therefore,
dopants should be selected based on the priorities of a specific application.
The research performed on doped MoS2 coatings over the past few decades has clearly
demonstrated their great promise. However, as with all new technologies, there are challenges
and opportunities. First, scalability is an issue for some deposition techniques [175], which can limit
the potential applications for which doped MoS2 may be considered. Second, not all elements can
be used for doping, since doping layered structures with elements that exhibit competing bonding
coordination can lead to formation of 3D as opposed to layered structures [175]. Third, and probably
most significant, massive amounts of testing will be required before sufficient data are available for
doped MoS2 coatings to be widely used in engineering applications. One limitation to broad testing is
that head-to-head comparison of tribological properties is challenging because different coatings are
often produced using different deposition techniques and under inconsistent conditions [202]. Testing
for a broad range of applications is also hindered by the fact that many of those applications will
operate in extreme environments for long durations (e.g., decade-long space missions in vacuum and
extreme temperatures); these conditions are difficult to reproduce in a lab setting. Another challenge is
lack of availability of doped MoS2 coatings with controlled composition and deposition. Only a few
Lubricants 2019, 7, 57 24 of 35

research labs have the equipment and experience to produce such materials and, while some coatings
(Ni-doped and Sb2 O3 /Au-doped) are commercially available, details about deposition conditions or
composition are not usually openly shared. Lastly, given the limitations of experimental testing and
the fact that the mechanisms by which these coatings perform their function is hidden from view (i.e.,
“buried”) in sliding interfaces, simulations would be an ideal tool for exploration. However, such
simulations require empirical potentials to describe the interatomic interactions and, to model wear,
require reactive potentials (which capture bond formation and breaking). At this point, there is no
reactive potential available for MoS2 with commonly used dopants. The development of such a model
would enable the direct interrogation of doped MoS2 sliding mechanisms, which could provide the
knowledge base necessary to tune dopants in order to provide optimized tribological properties for
specific applications.

7. Conclusions and Outlook

This review provided a focused overview of solid lubrication with MoS2 , starting from the
fundamentals of its structure and synthesis, followed by an analysis of the conditions under which
its use as a solid lubricant is advantageous, and corresponding tribological applications. The current
understanding of the fundamental mechanisms underlying the low friction and wear properties
of MoS2 was discussed in detail, as well as the dependence of these properties on the operating
environment and temperature. Finally, the structure and tribological properties of doped MoS2 were
reviewed. The main conclusions of the review and thoughts on emerging research directions are
provided below.
There is now agreement regarding the fundamental mechanisms responsible for the lubricative
character of MoS2 , namely the ability of its basal planes to orient themselves parallel to the sliding
direction during sliding and the low shear strength of the interface between basal planes, facilitating
inter-plane sliding with minimal frictional resistance to motion. Despite this general agreement, the
conclusions are based mostly on investigating MoS2 surfaces after the sliding experiments, which
does not provide a direct means of studying the details of the dynamic behavior of MoS2 during
sliding. As such, great strides in our understanding of MoS2 solid lubrication can be made by devising
new experimental methods that provide an in situ, high-resolution view of the sliding interface in a
MoS2 -lubricated contact. While this would be certainly a long-term goal, such an approach would also
provide concrete answers to questions about how wear occurs in MoS2 . Recent cross-sectional TEM
work performed on isolated MoS2 flakes is promising in this regard and future work could build on
this achievement to focus on MoS2 coatings that are more application-oriented.
Research shows that the tribological behavior of MoS2 is highly sensitive to operating conditions.
Based on growing interest in the use of MoS2 in aerospace/space applications where components
are expected to operate in a wide range of temperatures (from the cryogenic to several hundred
degrees Celsius) and in different environments, the temperature and environmental dependence of the
tribological properties of MoS2 has been the subject of many studies. In particular, the presence of water
or oxygen degrades the excellent lubricative properties of MoS2 observed in vacuum environments.
While some studies show that water adsorption plays an important role in the deterioration of the
tribological properties of MoS2 around room temperature, at higher temperatures oxidation was shown
to be responsible for diminishing tribological performance. Generally, in vacuum environment and
in the absence of wear, friction has been found to decrease with increasing temperature as predicted
for a thermally activated process. Wear rate, however, has been found to increase as the temperature
increases. Despite agreement regarding the effect of the operating environment and temperature on the
tribological properties of MoS2 , there are still significant discrepancies in the proposed mechanisms,
mostly due to difficulties associated with studying different environmental factors (e.g., the presence
of water, oxygen or other species) in an isolated fashion as well as design and construction of new
experimental setups that would allow extended tests of lubricants at extreme temperatures. Systematic
experiments conducted in well-controlled environments, as well as detailed atomistic simulations
Lubricants 2019, 7, 57 25 of 35

employing realistic interaction potentials, can thus provide insight into the structural and chemical
changes that occur at the buried sliding interface, which can eventually enable MoS2 to operate reliably
in varying environmental conditions.
The improved tribological performance exhibited by doped MoS2 coatings when compared with
their pristine counterparts (in particular, under challenging environmental conditions) has enabled
their use in critical technologies, including, but not limited to those related to space exploration. Despite
this fact, significant limitations/challenges remain related to scalability, the range of materials that can
be successfully used for doping, and the lack of availability of relevant test setups that can successfully
simulate, for instance, decade-long missions under vacuum and at cryogenic temperatures. Moreover,
while the specific method of deposition and related parameters are known to affect the tribological
performance of doped MoS2 coatings significantly, systematic studies evaluating these relations do
not currently exist, in part due to the fact that details of composition and deposition of commercially
successful coatings are not openly shared. Given the experimental difficulties, simulations arise as
a viable route for (i) evaluating and understanding the properties of existing doped MoS2 coatings,
especially by studying the buried sliding interface not accessible to conventional experiments, and (ii)
predicting new dopants and doping strategies for improved performance. Naturally, the success of
such simulations will crucially depend on the availability of accurate, reactive interaction potentials,
the development of which could constitute an important direction of research in the near future.
Progress in doped MoS2 tribology will also benefit from advancement in experimental structural
characterization. Standard methods for the analysis of periodic crystals, with diffraction of X-rays,
electrons, or neutrons, can provide only limited and average information for heterogeneous structures.
Most doping studies have not conclusively identified the structure of the doped materials. More
work employing methods that can provide localized information (such as EXAFS and XPS, and
high-resolution STM, AFM, and TEM), in conjunction with DFT calculations, is needed to elucidate
dopant locations, local environments, and structural distortions. Study of vibrations by Raman and
infrared spectroscopy or neutron scattering, supplemented by theoretical studies, are also promising
ways to investigate signatures of dopant concentrations and environments. Correlation of detailed
structural characterization with tribology studies is needed to identify the structure-property-function
relations. Knowledge from the extensive literature on MoS2 doping for electronic and catalytic
applications can also be leveraged to provide new insight and ideas for tribology. Experimental
and theoretical work is then needed to better understand how dopants affect growth processes and
morphology, and how the resulting structures can be controlled, to target the structures found to be
beneficial to tribological performance.
The rapidly widening range of conditions in which mechanical systems and components have to
operate efficiently will certainly maintain and accelerate interest in solid lubrication in the near future.
Within this context, this review summarized the properties, applications and mechanisms of MoS2 as a
solid lubricant, with the aim of providing a snapshot of our current understanding of this material, as
well as inspire future research directions. Focused experimental and computational work are expected
to accelerate developments in this field, potentially providing new opportunities for solid lubrication
using MoS2 in applications that traditionally employ oils and greases.
Funding: This research was supported by the Merced nAnomaterials Center for Energy and Sensing (MACES)
via the National Aeronautics and Space Administration (NASA) grant no. NNX15AQ01. A.M. and M.R.V.
acknowledge support from the National Science Foundation, award # CMMI-1762384.
Conflicts of Interest: The authors declare no conflict of interest.
Lubricants 2019, 7, 57 26 of 35

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