Carbon 96 (2016) 411e420

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Fluorine and sulfur co-doped amorphous carbon films to achieve

ultra-low friction under high vacuum
Fu Wang a, b, Liping Wang a, *, Qunji Xue a
a
State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, PR China
b
University of Chinese Academy of Sciences, Beijing 100039, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Fluorine and sulfur co-doped amorphous carbon (a-C:S:F) films were synthesized from C2H2 and SF6
Received 3 June 2015 plasma mixture, and the bonding states of S and F in films were scrutinized. The a-C:S:F films exhibited a
Received in revised form more ordered carbon structure than hydrogenated films. The friction behavior of films was tested against
16 September 2015
GCr15 bearing steel balls under high vacuum (HV) conditions. Ultra-low steady-state friction coefficient
Accepted 22 September 2015
Available online 26 September 2015
(0.01e0.02) was achieved for a-C:S:F films containing about 2.0 at.% H, depending on the concentrations
of S and F in films. Graphite-like transfer layer on the ball surface provided a low-adhesive sliding surface
terminated by eCF2- and eCF3 groups. The electrostatic repulsive interaction between the F-terminated
transfer layer and the S- and F-terminated carbon structure was probably responsible for the ultra-low
friction behavior. Intriguingly, the sp2-C clusters containing ‘thiophene-S’ (eCeSeCe) structure in films
might contribute to the low friction when sliding against an highly fluorinated surface. These results
demonstrate that the lubricating properties of a-C films in vacuum can be achieved through the S and F
co-doping, which is of great significance for developing a-C films as vacuum lubricants.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Amorphous carbon-based (a-C) films are very valuable tribo-
logical materials, and have been employed in some fields, including
automotive components, magnetic storage disks and infrared op-
tical windows [1,2]. Some impressive tribological behaviors can be
observed for various a-C films under certain conditions [3,4]. Under
ultra-high vacuum (UHV) environments, super-low friction coeffi-
cient (<0.01) is observed for highly hydrogenated amorphous car-
bon (a-C:H) films, which show great prospects as vacuum solid
lubricants. However, all the a-C films containing less than ~34 at.%
hydrogen usually exhibit rather high friction value (about 0.5e0.7)
under the same condition [5e10], which remarkably retards the
development of a-C films as vacuum solid lubricants. Thus far, there
still remain many challenges to develop vacuum-related applica-
tions of a-C films, and more attempts will be expected.
The super-low friction behavior of a-C:H films under UHV is
attributed to their atomically smooth and chemically inert surfaces.
The high levels of hydrogenation produces the high chemical
inertness in a-C:H film, where the dangling carbon s-bonds and the
* Corresponding author.
E-mail address: lpwang@licp.cas.cn (L. Wang).
growth of C-sp2 phase are limited. Thus a large decrease in strong
adhesion bonding that causes high friction and the weak van der
Waals force at sliding interfaces allow the super-low friction
behavior [11e16]. Limited shear occurring within the transfer layers
that may be formed on the uncoated counterparts also contribute
to the low friction [16e18]. Experimental evidences remarkably
support the aforementioned passivation hypothesis [19e21]. The H,
O and OH passivation of carbon materials can satisfactorily explain
the dependence of their friction on test environments and condi-
tions [20e22]. The H- or OH-terminated diamond model signifi-
cantly reduced adhesion and friction between contact surfaces
[23,24].
The low friction of a-C films can be achieved by controlling
chemistry of their bulk or near surface, or interface tribochemistry
[4]. Friction properties of various elements (Ti, Cr, W, Si, N, F, etc.)
doped a-C films were widely investigated in air, but few experi-
ments consider their friction behavior in vacuum because of their
infeasibility. And yet, theoretically, some non-metal elements (be-
sides H), O, F, S, N, etc., can also terminate dangling carbon s-bonds,
and consequently reduce adhesion and friction of a-C films.
Nevertheless a basic understanding about the vacuum friction
properties of these films is still lacking. Fluorinated a-C film ach-
ieved super-low friction value of 0.005 under UHV [25,26]. Multiple

http://dx.doi.org/10.1016/j.carbon.2015.09.084
0008-6223/© 2015 Elsevier Ltd. All rights reserved.
412 F. Wang et al. / Carbon 96 (2016) 411e420

doped a-C:H:Si:O:F film exhibited low friction coefficient (0.08)

against aluminum ball under vacuum, and a transfer layer passiv-
ated by eH, eF and eOH groups was evidenced [27]. Compared
with the H-terminated DLC model, the F-terminated DLC model
showed lower friction because of stronger repulsion between F
atoms [28,29]. In particular, incorporating S and F into a-C:H film
considerably improved vacuum friction properties of a-C:H films,
and the formation of CeS bonds appeared very important [30,31].
These results imply increasing opportunities for further developing
a-C films as vacuum lubricants by non-metal doping. Detailed
experimental investigations on this subject become very necessary
to understand the structure, properties, and vacuum friction
mechanism of these films.
In this paper, we investigate the F and S passivation of a-C films
towards their vacuum lubricity. Films were deposited from the
plasma mixture of C2H2 and SF6. The structure and composition of
films were determined by Raman spectra, XPS and ToF-SIMS
techniques. Their friction properties were assessed under high
vacuum (HV) conditions. In order to understand their underlying Fig. 1. Cross-section SEM image of a-C:S:F-4 film deposited on Silicon substrate. (A
friction mechanism, the nature of the transfer layer on steel ball colour version of this figure can be viewed online.)
was scrutinized. Finally, it is emphasized that incorporating F and S
into carbon-based network is highly significant for achieving their
low friction under HV conditions. of-flight secondary-ion mass spectrometry (ToF-SIMS) measure-
ment was performed in a ToF-SIMS IV instruments using 30 keV Biþ
2. Experimental details primary ions. Cross-section TEM sample taken from steel ball sur-
face covered with the transfer layer was prepared using focussed-
2.1. Materials ion beam (FIB) milling technique, and was observed by FEI Tecnai
F300 high-resolution transmission electron microscopy (HRTEM).
The samples were deposited on the Si (100) and highly polished
304 stainless steel substrates by parallel-plate hollow cathode 2.3. Friction and wear
plasma-enhanced chemical vapor deposition (PH-PECVD) system
with a base pressure of better than 2.0
103 Pa. Acetylene (C2H2) Friction behavior was evaluated using a home-built vacuum
and sulfur hexafluoride (SF6) were used as precursors. The sub- tribometer with rotational ball-on-disc configuration, equipped
strates were first cleaned ultrasonically using acetone and ethanol with frictional force sensor with accuracy rating of 0.01%. The
for 20 min, respectively. Before film deposition, the substrates counterpart was GCr15 bearing steel ball with diameter of 3.17 mm
underwent Arþ sputter cleaning procedure and thin amorphous (Hardness ¼ ~8.0 GPa, announced mean roughness ¼ 0.02 mm),
silicon interlayer (~80 nm) was deposited to enhance film adhesion. sliding tests were performed under HV (from 1.0
104 to
Si-containing carbon layer (~500 nm) was derived from SiH4 and 4.0
104 Pa) at room temperature. The rotational speed was
C2H2 as gradient layer. Then films were produced from the mixture 300 revs/min and rotational radius was 6.0 mm (linear speed:
of Ar, C2H2 and SF6 at a working pressure of 12 Pa. The samples were 0.19 m/s). The normal load was 1.0 N, corresponding to the initial
denoted as a-C:S:F-1, a-C:S:F-2, a-C:S:F-3 and a-C:S:F-4, corre- mean contact pressure (calculating from a Hertzian model) of 214,
sponding to source gases flow ratios (C2H2:SF6/sccm) of 50:40, 284, 388 and 445 MPa for a-C:S:F-4, a-C:S:F-3, a-C:S:F-2, a-C:S:F-1,
50:60 50:80 and 50:100, respectively. A pulsed-DC source supplied respectively. Sliding tests were repeated three times with the same
the power to gases discharge (voltage, 1.0 kV; pulse frequency, results. The wear volume of film was calculated by multiplying the
1.5 kHz; pulse duty ratio, 30%). Besides, F-containing a-C film (a- cross-sectional area of the track measured using a profile-meter
C:F:H) was also deposited from C2H2/CF4 under similar conditions (KLA-Tencor, D-100) by the circumference of the track. The wear
and a-C:H film was produced from C2H2 utilizing lower voltage, e volume of steel ball side was calculated as follow:
0.8 kV. Fig. 1 shows a fundamental structure pattern of a-C:S:F


2 
films. The total film thickness is about 2.0 mm according their cross- ph 3d
V¼ þ h2 (1)
section images. 6 4

2.2. Characterizations sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

d2
h ¼ r  r2  (2)
Raman spectra were recorded with a LabRam HR800 Jobin-Yvon 4
spectrometer with an excitation wavelength of 532 nm. The X-ray
photoelectron spectroscopy (XPS) was performed using a Thermo where d is the wear scar diameter, r is the radius of the steel ball.
Scientific ESCALAB 250Xi instrument equipped with a mono-
chromatic Al Ka (1486.8 eV) X-ray source. Binding energies were 3. Results and discussion
calibrated using the C 1s peak (284.8 eV). The hardness (H) and
Young's modulus (E) of the films were determined by the TI-950 3.1. Bonding characteristics of films
Tribolndenter equipped with a Berkovoich shape indenter. The
scanning electron microscopy (SEM) (JSM-5600LV) equipped with XPS was employed to investigate the elemental bonding states
energy-dispersive X-ray spectroscopy (EDS) and the field-emission in film a-C:S:F-4. In order to determine accurately fluorine chemical
SEM (Hitachi FE-SEM S4800) were used to examine the contact states, an Arþ ion etching step was conducted to remove the oxide
surfaces and the cross-section images of films, respectively. Time- layer on top surface. Fig. 2a shows the full-range XPS spectra of a-
 F. Wang et al. / Carbon 96 (2016) 411e420
C:S:F-4 film. The O 1s peak disappears after Arþ etching 2 min,
which indicates that oxygen species existed only on film surface.
High resolution C 1s spectrum in Fig. 2b can be fitted with five
component peaks at 284.8, 286.0, 287.5, 289.8 and 292.1 eV, typi-
cally assigned for the eCeH/eCeCe, eCeSe, eCeCFe, eCFe and
eCF2- functional groups, respectively [32e34]. It is clear that the
major form of F in film was the eCFe group, mono-fluorinated C
atom. A large proportion of eCeCFe group suggests that most
mono-fluorinated C atoms were not directly connected to each
other, namely, a partly fluorinated carbon-based network. The F 1s
peak at 687.2 eV (Fig. 2c) further indicates the eCFe groups.
With respect to sulfur element, we have little knowledge of its
bonding configurations in amorphous carbon films. Sulfur and
carbon can form various possible structures, including thiols
(ReSH), aromatic and aliphatic sulfides (ReSxeR) and thiophenic
structures. It is well known that thiophenic structures with a p-
electron conjugated system are significantly more stable than thiols
and sulfides. This agrees with the bond dissociation energy (BDE)
data of CeS bonds, 300e370 kJ/mol for thiols and sulfides, a
calculated value 560 kJ/mol for thiophene [35,36]. And when
merged into some aromatic systems, the reactivities of thiopenic
structures markedly decrease in the order of thiophenes >
benzothiophenes > dibenzothiophenes [37]. Therefore, the energy
ion bombardments and relatively high plasma temperature
(200e250  C) would preferentially support the stable thiophenic
structures during film deposition. What's more, a-C:H film consists
of sp2-bonded planar carbon clusters (aromatic ring) embedded in
a randomly oriented sp3-bonding matrix, some of the cluster
boundaries are decorated by H [38]. Thus the growing planar sp2-C
cluster boundaries decorated by S would favorably form the thio-
phenic structures, which stabilized the growing sp2 clusters and
prevent energy ions from further decomposing sp2 phases. High
resolution S 2p spectrum in Fig. 2d can be resolved into two peaks
at 163.7 and 164.9 eV, which were assigned to the S 2p3/2 and S 2p1/
Fig. 2. (a) Full-range XPS spectra of film a-C:S:F-4 before and after Arþ etching, high resolution XPS spectra of (b) C 1s, (c) F 1s, (d) S 2p after Arþ etching 2 min. (A colour version of
this figure can be viewed online.)
413
2 position of ‘thiophene-S’ respectively [39,40]. Consequently, sul-
fur in a-C:S:F film was primarily merged into the planar sp2-C
clusters in form of ‘thiophene-S’, and could terminate the formed
dangling C s-bonds at sp2 cluster boundaries in form of ring CeSeC
bond. With the incorporation of F and S, thus, a-C:S:F films pro-
vided a terminated carbon structure, which was expected to reduce
adhesion and friction in vacuum.
The changes in film microstructures were recorded using Raman
spectra. The spectrum of a-C:H film was also collected as a refer-
ence. All films show typical a-C feature (Fig. 3), an asymmetric peak
between 1000 and 1700 cm1, which can be decomposed into two
Gaussian peaks: D peak around 1360 cm1 corresponding to the
sp2-C organized in delocalized rings and G peak around 1560 cm1
corresponding to the total sp2-C [41,42]. The fitting parameters of
experimental Raman spectra in Fig. 3 are listed in Table 1. Due to
varied deposition conditions, the spectrum of a-C:H film is not
comparable with others. Incorporating F into carbon structure
usually causes the D peak to increase [32], and here a high ID/IG
ratio of 1.90 is observed for a-C:F:H film. The higher ID/IG values of
2.27 and 2.39 are noted for a-C:S:F-1 and a-C:S:F-4, respectively.
High ID/IG value for a-C:S:F-1 film should largely be ascribed to the S
incorporation since it contained 2.5 at.% F (Table 2). The stable
thiophenic structures mentioned above might allow such a large
increase in ID/IG, namely, increasing number or size of sp2 phase
clusters in carbon matrix. The high G peak position is related to
increasing sp2 phase and short, strained C]C configuration [41].
Sulfur doping slightly shifted down the G peak frequency compared
with fluorine doping, suggesting that a more relaxed carbon
structure could be obtained by the addition of S. The FWHM (G)
measures structural disorder arising from bond length and bond
angle distortions [41], the more perfect or less strained the sp2
clusters, the smaller the FWHM (G) value. The largest FWHM (G)
value was observed for a-C:F:H film (172 cm1), conversely, the
smallest FWHM (G) value originated from a-C:S:F-1 film
414 F. Wang et al. / Carbon 96 (2016) 411e420

Fig. 2a, approximately 8.0 at.% O was detected on the as-deposited

film surfaces, but the O content was less than 1.0 at.% in the bulk of
film. Hydrogen is a decisive factor that affects vacuum friction
properties of a-C:H films, but lack of a direct measurement. Based
on our previous result, a-C:H film containing 9.8 at.% H was syn-
thesized from a C2H2 plasma (Ar: 100 sccm, C2H2: 150 sccm) uti-
lizing the same PECVD systems (voltage: 0.8 kV, pressure: 3.4 Pa)
[44]. In investigated films, the a-C:Si:H layer was produced under
quite similar conditions (Ar: 100 sccm, C2H2: 150 sccm, SiH4:
5 sccm, voltage: e 0.8 kV, Pressure: 3.8 Pa), thereby about 10.0 at%
H. Comparing the intensity of H, CH and C2H ions from a-C:S:F
film with that from a-C:Si:H layer in Fig. 4, it is rationally speculated
that the H in a-C:S:F-4 film is about 2.0 at.% or less. For a-C:S:F films,
it is understandable due to lower proportion of H in precursor,
complete ionization of C2H2, Arþ bombardment and especially
chemical etching of F (removing H in form of HF [45,46]). Thus, H
exerted a negligible influence on friction properties of a-C:S:F-4
film.
ToF-SIMS depth profile analysis in Fig. 4 shows the bulk nature
Fig. 3. Raman spectra of a-C:H, a-C:F:H, a-C:S:F-1 and a-C:S:F-4 films. (A colour of a-C:S:F-4 film that is crucial for its friction performances under
version of this figure can be viewed online.)
HV conditions. The almost stable F intensity represents saturation
in the detector signal, rather than a constant F content. We can not
accurately speculate the F distribution in film as the depth, but high
Table 1 F concentration in the bulk is definite. The high F/H (6/1) atomic
Peak parameters of films obtained through fitting experimental Raman spectra in
ratio (6SF6/2C2H2) in source gases also permitted incorporating F
Fig. 3.
into the bulk [47]. The intensity of S, CH and C ions changes with
Sample G position/cm1 Area ratio Full width at half maximum (G) the depth. This could be associated with changed plasma nature
ID/IG FWHM (G)/cm1
(monitoring current varied from 0.64 A to 0.46 A) due to the growth
a-C:H 1528 1.32 159 of insulator film and therefore microstructural changes. The CH
a-C:F:H 1547 1.90 172 ion in a-C:S:F film layer, only H-containing signal, also indicates low
a-C:S:F-1 1543 2.27 146
a-C:S:F-4 1540 2.39 152
H content. The trace oxygen was also discovered throughout the
whole film. Therefore, the F and S co-doped carbon structure
allowed us to consider merely the influence of F and S on friction
behavior under HV conditions.
Table 2
The surface compositions of samples obtained from XPS measurements.

Sample C (at.%) F (at.%) S (at.%) 3.3. Frictional behavior under high vacuum conditions
a-C:F:H 83.2 16.8 e
a-C:S:F-1 88.9 2.5 8.6 Fig. 5 shows the representative friction coefficient curves, and
a-C:S:F-2 83.5 7.9 8.6 quite different friction behaviors are observed relying on the F and S
a-C:S:F-3 80.5 11.5 8.0 contents in films. The a-C:F:H film exhibited a high friction value
a-C:S:F-4 74.8 15.8 9.3 ~0.38 and failed after ~3500 sliding cycles. Similar friction perfor-
mances were observed for a-C:S:F-1 and a-C:S:F-2, both of which
were worn out after transient sliding, only more sliding cycles for a-
(146 cm1). This suggests that incorporating F into carbon network
led to more distorted or more strained sp2-C clusters, which could
be associated with the larger electron-negativity and atomic radii
(58 pm) of F atom in comparison with H atom (32 pm). However,
the incorporation of S caused structural ordering, relived the stress
felt by C]C bonds and promoted the formation of C]C bonds
organized in delocalized rings. In brief, amorphous carbon-based
network became more ordered and relaxed with introduction of
sulfur.

3.2. Chemical composition of films

The surface compositions of samples were determined by XPS,

and are summarized in Table 2. Accidentally, the a-C:S:F films
showed similar S contents and varied F contents from 2.5 to 15.8
at.%, which is conducive to the subsequent discussion on friction
mechanism. The a-C:F:H film contained 16.8 at.% F, slightly higher
than that of a-C:S:F-4 film. This study aimed to investigate the in-
fluence of F and S on vacuum friction behavior of a-C film and
therefore the existence of O and H in film was undesirable. Surface Fig. 4. Depth profile of secondary ion intensities versus Biþ sputter time for the a-
O contamination is usually observed for a-C films [43]. According to C:S:F-4 film. (A colour version of this figure can be viewed online.)
 F. Wang et al. / Carbon 96 (2016) 411e420
Fig. 5. Friction curves for films a-C:F:H, a-C:S:F-1, a-C:S:F-2, a-C:S:F-3 and a-C:S:F-4
against GCr15 balls under HV. (A colour version of this figure can be viewed online.)
C:S:F-2. Both a-C:S:F-3 and a-C:S:F-4, containing higher F contents,
achieved ultra-low steady-state friction coefficient 0.01e0.02, and
meanwhile a super-low friction value (~0.005) was observed at
initial sliding stages. The super-low friction was ascribed to the fully
terminated surface covered by H, F, S and some O-containing
groups. Before reaching the ultra-low friction level, an increasing
friction value could be associated with the formation of the transfer
layer responsible for ultra-low friction. The tribochemical reactions
and the formation of wear particles at sliding interface led to minor
friction fluctuation. As shown in Fig. 8a, a considerable amount of
wear debris was piled around wear scar.
Under HV environments, sliding resistance in solid contact is
primarily controlled by the adhesion [48], which is closely related
to the physical and chemical natures of sliding couples. Table 3
summarizes the fundamental physical properties of films. Films
showed decreasing hardness (H) and elastic modulus (E) as the
incorporation of F and S, and surface roughness Ra < 10 nm.
Apparently, the mechanical properties of films were not essential
for achieving vacuum low friction. As seen in Fig. 5, friction
behavior depended strongly on the chemical composition of films.
For a-C:S:F films containing ~8.5 at.% S, the achievement of ultra-
low friction required higher F content (>11.0 at.%), just as a-C:S:F-
3 and a-C:S:F-4. However, a-C:F:H film with high F content
exhibited high friction value, suggesting that S doping played a
crucial role in reducing friction to ultra-low level and led to more
enduring sliding. Based on these results, we recognize that a judi-
cious combination of F and S within films becomes particularly vital
to obtain intrinsic lubricity of a-C films. Depending on the varied S
content in film, different threshold in F content may be required to
achieve ultra-low friction under HV.
Preliminary process optimization was conducted to ameliorate
the film properties. The working pressure, substrate voltage or Ar
flow was regulated to alter film natures. Friction properties of as-
deposited films are presented in Fig. 6. Film deposited from work-
ing pressure of 12 Pa and Ar flow of 100 sccm provided the longest
wear life, exceeding 80000 sliding cycles. The structures and
Table 3
Fundamental physical properties of a-C:S:F films and fluorinated film.
Sample a-C:S:F-1 a-C:S:F-2 a-C:S:F-3 a-C:S:F-4
H/GPa 8.6 6.8 3.7 2.6
E/GPa 77.9 59.4 33.6 20.8
Ra/nm 8.01 6.98 6.97 5.37
415
properties of a-C film strongly depend on the energy (E) of
impacting ions, which is controlled by deposition parameters of
PECVD system: E f VB/P1/2, where VB is the self-bias voltage, P is
the working pressure [1]. The substrate voltage below e 1.0 kV did
not obtain desirable film due to inefficient ionization of SF6. Owing
to strong ions etching, F content in films decreased by 2.0 at.% e 4.0
at.% with the pressure decreasing. Low pressure (high ion energy)
simultaneously induces high film compression stress that affects
the friction performances of films [49], but it is difficult to comment
the film stress precisely. Local exfoliation resulting from high
compression stress was observed for the films deposited under
lower pressures. High compression stress and the decrease in F
content could therefore result in the deterioration of film proper-
ties, as films of 6, 8 and10 Pa.
3.4. Analyses of sliding interface
3.4.1. Structure and chemistry of transfer layer
Based on the chemical nature and the easy shear ability of
transfer layer, the friction responses of a-C film may vary a great
deal [16]. After 60 min of sliding against a-C:S:F-4 film, Raman
spectra were collected from transfer layer, wear track and wear
debris (Fig. 7a). Raman spectrum of transfer layer clearly indicates
the presence of a carbonaceous layer, and partly separated G peak
and D peak reveal a graphite-like characteristic. Raman spectrum of
wear track resembles that of as-deposited film (Fig. 3), only a
slightly enhanced D peak in wear track. This could be associated
with the thin transformation layer (~10 nm) on the surface of wear
track, which was beyond Raman detectability (probing depth:
50e100 nm for visible excitation). The spectrum in track thereby
reflects film bulk nature and it is difficult to recognize this minor
change on track surface. This transformed layer might be squeezed
out the track region and became part of wear debris. The enhanced
D peak in wear debris clearly indicates structural changes induced
by friction. The ultra-low friction behavior of a-C:S:F films could be
partly attributed to the easy shear ability of the transfer layer and
transformed layer. But it is too complicated to quantify their con-
tributions to low friction.
Chemical states of the transfer layer were determined by XPS.
High-resolution spectra of C 1s, F 1s, and Fe 2p are shown in
Fig. 7bed. Three new peaks appear at C 1s binding energies of
292.5, 293.8 and 295.3 eV, corresponding to the eCF2-, eCF3 and
eCF2eCF3 functional groups, respectively [33,34]. The peaks at
a-C:F:H
11.9
Fig. 6. Friction curves for films deposited at working pressure 6 Pa, 8 Pa, 10 Pa, 12 Pa
122.7
(Ar:100 sccm), and Ar flow 150 sccm (12 Pa) against GCr15 balls under HV. (A colour
7.23
version of this figure can be viewed online.)
416 F. Wang et al. / Carbon 96 (2016) 411e420
Fig. 7. (a) Raman spectra of transfer layer, wear track and wear debris formed after 60 min of sliding against a-C:S:F-4 film, and corresponding high resolution XPS spectra of (b) C
1s, (c) F 1s and (d) Fe 2p on the transfer layer. (A colour version of this figure can be viewed online.)
286.5 and 288.9 eV are indefinite, and can be partly assigned to the
b position (first neighbors) of eCF2/CF3 groups [34]. But we can
not exclude the O-containing groups (CeOeC/CeOH: 286.4 eV, O]
CeOH: 288.9 eV [50]), since both the residual H2O in vacuum of
about 104 Pa and exposure to air during transferring sample to XPS
analysis chamber would cause impossible oxidation. The F 1s
spectrum (Fig. 7c) can be decomposed into three peaks at 684.8,
687.1 and 689.6 eV, assigned to the FeF2, eCFe and eCF2/CF3
groups, respectively. The major peak at 689.6 eV suggests that F on
the surface of transfer layer mainly existed in the eCF2- and eCF3
groups. The weak Fe 2p peak (Fig. 7d) at 711.6 eV confirms the
presence of FeF2. There is no obvious S observed on the surface of
transfer layer (Fig. 12). Based on the XPS analysis, the surface of the
transfer layer composed of 68.3 at.% C, 27.1 at.% F, 2.5 at.% S and 2.0
at.% Fe, a significant F accumulation. This means that the transfer
layer provided an highly fluorinated carbon surface with eCF2/
CF3 groups, which possessed low surface energy, favoring low
adhesion.
The accumulated F atoms on the transfer layer surface is very
important for achieving ultra-low friction of a-C:S:F film, and it was
also observed for a-C:F:H film sliding against aluminum or mag-
nesium alloy [51]. Although it is quite difficult to break CeF bonds
(BDE: 450e550 kJ/mol [36]) under thermodynamic conditions, the
rubbing can facilitate the CeF bond cleavage due to mechanical
strains, triboemission and friction heat [52]. Furthermore, it had
been found that triboemission intensity increased with increasing
electric resistance of solid [53]. The insulator properties of a-C film
can thereby promote this process and the CeF bond breaking. The
cleavage of CeF bond was noticed in tribochemical decomposition
of ionic liquids, where the formation of CFþ and FeF2/FeF3 origi-
nating from the cleavage of CeF bond in (SO2CF3)2N [54,55]. More
importantly, high reactivity of F atom may be responsible for their
accumulation on the transfer layer because the newly-formed
reactive sites at sliding interface may display strong affinity for
active F radicals or ions.
Fig. 8 presents the SEM image of wear scar and corresponding
EDS mappings after 60 min of sliding over a-C:S:F-4 film. A great
amount of wear debris is observed around the wear scar of about
200 mm diameter (Fig. 8a). This could be mainly attributed to severe
mechanical wear due to high film softness (2.6 GPa, Table 3). The
large-size wear particles further account for the mechanical wear.
The EDS mappings (Fig. 8bed) confirmed the overall variation of
elements induced by rubbing. The C and S signals were detected
uniformly over the whole wear debris, but a significantly weak F
signal in wear debris. This illustrates that F participated in tri-
bochemical reactions at sliding interface and was partly removed
from the carbonaceous structure with the generation of wear
debris. The CeF bonds could be broken more easily under rubbing
conditions because of higher reactivity of F atom. This also hints the
formation of the fluorinated transfer layer (Fig. 7). However, owing
to their stability, the sp2-C clusters containing thiophenic struc-
tures might be removed as a whole though breaking the relatively
weak CeC bonds (BDE: 400e460 kJ/mol [36]) linking sp2-C clusters
to sp3-C matrix. This may be the reason why S was remained in
wear debris, instead of transfer layer.
3.4.2. Wear tracks and wear behavior
The a-C:S:F-1 and a-C:S:F-2 films were completely removed
from steel substrates, accompanying by a sharp friction increase
(Fig. 5). After 60 min of sliding, SEM images of wear tracks for a-
C:S:F-3 and a-C:S:F-4 are showed in Fig. 9. Local exfoliation (Fig. 9a)
and clear cracks (Fig. 9b) are seen on the track regions. This could be
associated with unreliable adhesion of film to substrates. High-
resolution XPS spectra in Fig. 9c indicate the chemical states of
track surface for a-C:S:F-4 film. The C 1s (292.8 eV), F 1s (685.0 and
689.4 eV) and Fe 2p peaks show the existence of small qualities of
multi-fluorinated C atoms and iron fluoride, which detached from
the fluorinated transfer layer under rubbing actions. However, the
 F. Wang et al. / Carbon 96 (2016) 411e420
Fig. 8. (a) SEM image of wear scar formed after 60 min of sliding contact with a-C:S:F-4, and corresponding EDS mappings for (b) C, (c) F, and (d) S. (A colour version of this figure
can be viewed online.)
Fig. 9. SEM images of wear tracks formed after 60 min of sliding over (a) a-C:S:F-3 and
(b) a-C:S:F-4, (c) high-resolution XPS C 1s, F 1s and Fe 2p spectra taken from the area
marked by red dotted line in (b). (A colour version of this figure can be viewed online.)
417
wear track mainly reflected the intrinsic nature of film. The area
ratio of fitting peaks in F 1s spectrum (Fig. 9c) shows 12.0 at.% F in
eCFx-groups, suggesting a reduced F content in the bulk of film. In
contrast with a-C:S:F-4 (2.6 GPa), the wider track (270 mm) for a-
C:S:F-3 (3.7 GPa) illustrates that the wear resistance of films under
HV strongly depends on their compositions, and increasing F con-
tent in a-C:S:F-4 reduced wear. Owing to the build-up and repair of
the fluorinated transfer layer, film with relatively low F content
would thereby sacrifice larger volume to fulfill F demand, and
hence higher wear for a-C:S:F-3 film.
Considering local exfoliation of film layer in Fig. 9a, quantifying
wear of film was performed after 30 min of sliding test. The cor-
responding optical images and cross-sectional profiles of wear
tracks are shown in Fig. 10. The a-C:S:F-3 film showed higher wear
rate (1.24
106 mm3/Nm) than a-C:S:F-4 film (4.80
107 mm3/
Nm). According to equations (1) and (2), the wear rate of the steel
ball side was estimated to be 8.10
108 mm3/Nm from the wear
scar in Fig. 8a. This indicates that a-C:S:F film with high F and S
content provided low wear rate and the formation of fluorinated
transfer layer drastically reduced the wear of steel ball.
3.5. Roles of sulfur and fluorine in friction
Differing from H element, both F and S show high reactivity with
iron (Fe), signifying complex tribochemical reactions. A rough
judgment from the standard enthalpy of formation of iron (II)
fluoride and sulfide (△Hf0 (FeF2): 705.84 kJ/mol, △Hf0
(FeS): 100.42 kJ/mol, △Hf0 (FeS2): 171.54 kJ/mol) suggests that
steel counterpart would preferentially react with F within film. In
addition, lower BDE value for CeF bonds in comparison with ring
CeS bonds and higher F concentration in film also approves the
formation of FeF2. The F 1s and Fe 2p spectra in Fig. 7c and
d confirm the presence of FeF2 on the transfer layer. The high-
418 F. Wang et al. / Carbon 96 (2016) 411e420

Fig. 10. Optical images and cross-sectional profiles of the wear tracks produced after 30 min of sliding over (a) a-C:S:F-3 and (b) a-C:S:F-4. (A colour version of this figure can be
viewed online.)

resolution TEM image in Fig. 11 further provides the evidence for
the presence of FeF2 in the transfer layer. A clear FeF2 layer is
observed and clings to the surface of GCr15 ball. It was proposed
that the formation of AlF3 at Al/transfer layer interface promoted
the build-up of carbon transfer layer [27]. We consider that the FeF2
at Fe/transfer layer also conduced to the formation of the transfer
layer and could reduce subsequent adhesion between film and steel
counterpart.
Friction curves in Fig. 5 show that the F was essential for a-C:S:F
films to achieve ultra-low friction under HV. Considering the
passivation, the F atom in carbon structure is similar to H, but the
friction behavior of fluorinated a-C films under HV has been rarely
reported. Fluorinated carbon surfaces are considered to be greater
potential as low friction surface than hydrogenated ones because of
stronger repulsion between F atoms [28,29]. A fully F-terminated
diamond surface was entirely covered by charges (electron den-
sity > 0.1) and more effectively blocked strong CeC covalent in-
teractions across sliding interface [28,56]. The larger electro-
negativity and size of F atom may therefore enhance its passiv-
ation ability. As reported by Fontaine et al., the super-low friction
(0.005) was achieved by fluorinated a-C film with 18 at.% F þ 5 at.%

Fig. 12. High resolution S 2p spectra of film, wear track, wear debris and transfer layer
Fig. 11. High-resolution transmission electron microscopy (HRTEM) image of transfer after 60 min of sliding against a-C:S:F-4 film. (A colour version of this figure can be
layer/GCr15 ball interface formed after sliding against a-C:S:F-4 film. viewed online.)
 F. Wang et al. / Carbon 96 (2016) 411e420
Fig. 13. Schematic description of the sliding interface for achieving ultra-low friction of a-C:S:F films under HV. (A colour version of this figure can be viewed online.)
H [26] against a steel surface under UHV, a reduced demand for
passivation atoms (23 at.%, markedly less than 34 at.% for a-C:H
films). Besides the tribochemical reactions, stronger passivation
ability of F atom might reasonably explain such a distinction.
Fluorinated carbon network is thereby more beneficial to provide a
fully passivated surface. In this paper, 16.8 at.% F in a-C:F:H film
could not completely shield strong CeC bond adhesion, which
hindered the formation of the fluorinated transfer layer, and hence
high friction value. But the formation of FeF2 at sliding interface
might retard the film failure due to impeding the strong adhesion
to some extent. Accordingly, regarding fluorinated a-C films,
despite possible favorable tribochemical reactions, a sufficiently
passivated carbon network is still crucial for achieving their low
friction under HV. For the investigated a-C:S:F films, however, more
than 11 at.% F was required to produce a desirable carbon structure.
Sulfur is another contributor to the ultra-low friction in the a-
C:S:F films. Compared with the a-C:F:H film, the existence of S in a-
C:S:F films directly reduced friction value to ultra-low level and
reduced the demand for F atoms. Meanwhile, the S-doping a-C:H
film with less than 30 at.% H also obtained low friction under HV
and allowed more enduring sliding due to the strong CeS bond
(BDE in diatomic molecules: CeS: 713, CeC: 618, CeF: 514, CeH:
338 kJ/mol) [30,31]. Therefore, the low friction under HV was
likewise achieved by S-doped a-C film containing less F or H atoms.
In order to understand underlying friction mechanism, high-
resolution XPS S 2p spectra are shown in Fig. 12. The S 2p peaks
in wear track and wear debris are almost identical to that of as-
deposited film. As discussed above, these peaks can be assigned
to the ring CeS bonds in thiophenic structures. The transfer layer
shows a very feeble S 2p peak (Fig. 12). This suggests that there
were no obvious changes in CeS bonds during rubbing. This can be
explained by high reactivity of F atom and stability of thiophenic
structures. Especially, with the formation of the fluorinated transfer
layer, ‘thiophenic-S’ would reveal lower reaction tendency towards
fluorinated surface. The sp2-C clusters containing ‘thiophene-S’, as
a whole, were separated from the sp3-C matrix and agglomerated
into wear debris due to lower CeC bond strength. Now the ‘thio-
phene-S’ in films, on the one hand, terminated many sp2-C clusters
and thereby decreased cross-link density of carbon-based network.
The hardness and wear resistance of films deteriorated. On the
other hand, the ‘thiophene-S’ intrinsically eliminated C s-bonds at
sp2 cluster edges and stabilized the clusters. These stable clusters
would reduce the production of the carbon dangling C s-bonds
during friction. And numerous stabilized planar sp2 clusters hold-
ing delocalized p-electron systems would show low adhesion to-
ward highly fluorinated transfer layer.
According to the above statements, a proposed interface model
is shown in Fig. 13. Owing to the elemental difference in electro-
negativity (F-3.98, S-2.58, C-2.55, H-2.2), both CeF bonds and
delocalized p-systems in sp2-C clusters containing ‘thiophenic-S’
can allow the negatively charged surface. Therefore, the electro-
static repulsion between highly fluorinated transfer layer and S-
and F-terminated carbon structure may be a major reason for the
419
ultra-low friction. Consequently, based on current understanding,
fluorine and sulfur co-doping may be of great significance for
developing vacuum-related applications of a-C films. And fortu-
nately, the deterioration of film mechanical properties can be
improved by the further design of film structure and composition
modification.
4. Conclusions
In summary, we have synthesized and investigated fluorine and
sulfur co-doped a-C films. It is demonstrated that the ultra-low
friction behavior of a-C films under HV can be achieved by the S
and F co-passivation, not confined to the H passivation. The stable
thiophenic structures merged into the sp2-C clusters have been
identified as the likeliest form for S atom in films, which promoted
the formation of more ordered carbon structure and contributed to
the low friction. Both the delocalized p-system containing ‘thio-
phene-S’ and CeF bonds can allow forming negatively charged
surface, and thereby the electrostatic repulsion between sliding
surfaces achieve low adhesion and ultra-low friction. Considering
the tribochemical reactions, stronger passivation ability, and the
thiophenic structures, we believe that a judicious combination of F
and S elements in film, in particular, a series of a-C:S:F films with
slightly lower than 8 at.% S will be expected to produce more
valuable films for possible applications. More importantly, this
study explores new pathways for ameliorating the intrinsic lu-
bricity of a-C films. Multi-nonmetal doping is a promising approach
to design and develop a-C films as vacuum lubricants.
Acknowledgments
This work was supported by the State Key Project of Funda-
mental Research of China (2013 CB 632302) and the National
Natural Science Foundation of China (Grant No. 51322508).
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