Surface & Coatings Technology 445 (2022) 128716

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Effect of low-pressure deposition on the mechanical and tribological

properties of a-C:H films deposited via modified pulsed-DC PECVD with
active screen as an additional cathode
A. Capote a, *, G. Capote b, E.J. Corat a, V.J. Trava-Airoldi a
a
Instituto Nacional de Pesquisas Espaciais (INPE), Laboratório Associado de Sensores e Materiais (LABAS), Avenida dos Astronautas 1758 - São José dos Campos,
12227-010, SP, Brazil
b
Universidad Nacional de Colombia, Facultad de Ciencias, Departamento de Física, Carrera 45, N. 26-85-Edificio Uriel Gutiérrez, Bogotá D.C., Colombia

A R T I C L E I N F O A B S T R A C T

Keywords: Due to their attractive mechanical, chemical, tribological, and biological properties, diamond-like carbon (DLC)
Diamond-like carbon coatings are widely used in many industrial applications. Normally, the deposition of amorphous hydrogenated
Deposition pressure carbon (a-C:H) films is obtained via the plasma-enhanced chemical vapor deposition (PECVD) technique.
PECVD
Recently, a modified pulsed-DC PECVD technique has attracted attention in this field due to its making it possible
Additional cathode
Tribology
to grow a-C:H films at low-pressures (up to 0.1 Pa) in a collision less regime, leading to the achievement of
Mechanical properties improved mechanical and tribological properties. The incorporation of an additional cathode allows the
confinement of electrons and ions, stabilizing and densifying the cold plasma at much lower pressure than
conventional PECVD systems. This method is distinguished by higher energy and acceleration of the C+ ions,
simpler reactor system equipment, and lower operating cost. In the present investigation, hydrogenated amor­
phous carbon films were grown on AISI 316 stainless steel using a thin amorphous silicon interlayer to improve
interface adherence. The characterization of the coatings allowed identifying the influence of the deposition
pressure on the microstructural, mechanical, and tribological properties and the film's adherence. The main
results indicate that obtaining films with high hardness, low compressive stress, low coefficient of friction, high
wear resistance, and appropriate adhesion is possible at deposition pressures almost 100 times lower than
conventional PECVD techniques.

1. Introduction
Hydrogenated amorphous carbon (a-C:H) films are part of the
Diamond-Like Carbon (DLC) coatings family. They have interesting
mechanical, tribological, and biological properties, among other char­
acteristics [1]. These films can be used in several applications due to
their high degree of hardness and wear resistance and low coefficient of
friction, in addition to their chemical inertness and biological compat­
ibility [2,3]. The allotropic nature of the carbon element allows the
formation of many multi-atomic crystalline and amorphous structures
with different contents of all three types of hybridization (sp3, sp2, and
sp) [1,2]. It is possible to classify DLC films according to the hydrogen
content and the variation of the sp3 (diamond-like) and sp2 (graphite-
like) carbon bonding ratio [4]. In general, a-C:H films are those with
hydrogen content between 20 and 60 % and up to 40 % of the C–C sp3
phase [4,5]. Amorphous carbon hard films can be grown using physical
vapor deposition (PVD) processes such as sputtering, pulsed filtered
cathodic vacuum arc deposition (PFCVAD), and many others [1,6].
Among the chemical vapor deposition (CVD) techniques, plasma-
enhanced chemical vapor deposition (PECVD) allows better tempera­
ture control of the substrates [3,7]. Normally, the properties of a-C:H
films grown by means of the PECVD technique strongly depend on the
process parameters, such as the pressure, bias-voltage, temperature,
dilution composition, and chemical nature of the precursor gases
[7–11].
In the modified PECVD technique, when an additional cathode or
active screen is incorporated, it is possible to achieve lower deposition
pressures with a near collision less regime between plasma species. In
addition, the cylinder shape dimension and grid transparency of the
additional cathode produces an electric field that allows the

* Corresponding author.
E-mail address: ariel.sanchez@inpe.br (A. Capote).

https://doi.org/10.1016/j.surfcoat.2022.128716
Received 21 April 2022; Received in revised form 4 July 2022; Accepted 5 July 2022
Available online 12 July 2022
0257-8972/© 2022 Elsevier B.V. All rights reserved.
A. Capote et al.
confinement of electrons and ions between the cathode surfaces [12,13],
thus increasing the ionization probabilities and producing a local in­
crease in the plasma density and therefore an increase in the tempera­
ture or energy of the species present in the plasma [14]. Under these
conditions, it is possible to obtain highly energetic ions with a narrower
energy distribution [12]. The formation of a cold plasma with high-
energy ions and high neutral species flux is important in a-C:H film
nucleation and densification [14–19]. Furthermore, this modified
technique has allowed improving the uniformity of the DLC coatings'
growth in complex three-dimensional geometries, obtaining high-
quality films with enhanced hardness and adhesion [10,12,13,20].
In order to obtain coatings that meet industrial specifications, it is
necessary to control the deposition parameters of the PECVD technique,
which have a great influence on the properties of the DLC films. In
general, predicting the influence of each parameter on the deposited
coating's properties is challenging, because of the possible nonlinear
behavior and the need to perform a large number of experiments
[21,22]. Additionally, the material used as substrate has a considerable
influence on the adherence of these films, and limitations are usually
due to the high residual compressive stress in the film's microstructure,
inherent in the deposition process [10]. Usually, the incorporation of an
amorphous silicon interlayer improves adherence between the substrate
surface and DLC coatings on metallic substrates [10,12,23,24].
In this study, DLC coatings were grown on AISI 316 stainless steel
substrates using the modified pulsed-DC PECVD technique with an
additional cathode. The influence of the deposition pressure, especially
within the studied low range (0.1 to 1.3 Pa), on the film's adherence and
the microstructural, mechanical, and tribological properties was
analyzed. The observed trends in the micro- and macro-scale properties
of a-C:H films showed that it is possible to obtain hard, low-stressed a-C:
H films, with a low coefficient of friction, high wear resistance, and
appropriate adhesion.
2. Experimental details
2.1. Sample preparation
AISI 316 stainless steel and silicon (100) were used as substrates for
the deposition of a-C:H coatings. Samples with 15 mm diameter and 6
mm average thickness were cut from a stainless steel bar. The upper
surfaces of the samples were prepared in a wet sanding process with
different grit sizes varying between 80 and 1200. Subsequently, the
samples were polished with a 5-μm diamond powder paste, obtaining an
average roughness of 15 nm. Additionally, the substrates were cleaned
in an ultrasound bath, using degreasing agents, deionized water, and
isopropyl alcohol before being placed in the reactor chamber.
2.2. Film deposition
The DLC films were obtained via the modified PECVD technique
combined with an additional cathode system, developed by DIMARE-
INPE (Brazil), for greater confinement of the electrons and ions
[10–13,20,25,26]. The pulsed-DC power source used has a fixed fre­
quency of 20 kHz with a controllable variable pulse width between 5 and
20 μs. Additionally, it is possible to choose the waveform amplitude in a
low-voltage range between − 100 and − 1500 V or in a high-voltage
range between − 1500 and − 15,000 V. A short positive pulse of
approximately 40 V is applied after the negative main pulse. This posi­
tive pulse favors the removal of molecules or charged particles that
accumulate on the substrate's surface, modifying the relative potential of
the surface with respect to the plasma and affecting the flow of ions
during the process [11,25,26]. The additional cathode used consists of a
cylindrical-shaped AISI 304 steel grid mesh. This grid can be designed to
act as an active screen in a fluctuating potential or as an extra cathode in
order to increase plasma densification. In this modified PECVD system,
the additional cathode and the sample holder main cathode were
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Surface & Coatings Technology 445 (2022) 128716
subjected to the same bias voltage. Due to the film's growth on both
cathode surfaces, a sand-blasting cleaning processes must be performed
before each deposition in order to guarantee the uniformity of the
electrode's electrical conductivity. A schematic representation of the
bipolar pulsed-DC PECVD system with an additional cathode is shown in
Fig. 1. A simplified piping and instrument diagram (P&ID) includes the
pumping system, consisting of a vacuum pump, used to obtain the pri­
mary vacuum, and an oil diffusion pump, which together allow reaching
internal pressures of up to 0.01 Pa. The presence of two pressure gauges,
one of the Pirani type (PT-1, for pressure transmitter) and the other of
the capacitance diaphragm type (PT-2), were used to monitor the
pressure inside the reactor chamber. The precursor gases are inserted
into the reactor with a mass flow control system. The system has several
valves along the reactor pipes, including manual actuation needle valves
(FCV-1, for the flow control valve) and pneumatic actuated valves (PCV-
1 and PCV-2, for the pressure control valve). Additionally, a butterfly
valve (PCV-3) arranged in the diffusion pump is actuated by a servo­
motor system.
First, an argon (Ar) plasma cleaning of the samples was performed at
low pressure (0.4 Pa), with 40 % duty cycle and bias voltage of − 600 V.
The Ar plasma acts on the surface, removing organic contaminants and
other molecules remaining on the substrate. The argon flow is main­
tained throughout the deposition process because it serves as a plasma
stabilizer for silane (SiH4) and acetylene (C2H2) [8]. The first deposition
step consists of the formation of a thin amorphous silicon (a-Si) inter­
layer on the substrate surface, leading to an increase in the interfacial
adhesion between a-C:H films and metallic surfaces [10,24,25]. This a-Si
thin film was obtained with a silane (4 sccm) precursor gas mixed with
argon (2 sccm) at low pressure (0.5 Pa), with a 40 % duty cycle and
applying a bias voltage of − 800 V. The second deposition step corre­
sponded to a transitional film layer between a-Si and a-C:H. This layer
was grown using argon (2 sccm) and acetylene (30 sccm) and a gradu­
ally decreasing silane mass flow (0.5 sccm per minute) as precursor
gases. This step was developed at a variable working pressure (P*) with a
40 % duty cycle and − 800 V bias voltage. For the final step, a-C:H film
deposition was performed at different working pressures within the 0.1
to 1.3 Pa range. The DLC film was deposited at a fixed 40 % duty cycle
and applying a bias voltage of − 800 V. The a-C:H films were deposited
using an Ar / (Ar + C2H2) flow ratio near 6 %; this value was chosen due
to the reported influence of the low gas dilution at less compressive
stress and higher ion penetration depth [8]. The main controllable
process parameters are shown in Table 1.
2.3. Characterization of coatings
After the deposition of the DLC coatings on the substrates, tests were
performed in order to determine the microstructural, mechanical,
tribological, and morphological properties. The microstructural prop­
erties were determined using the Raman spectroscopy and scanning
electron microscopy (SEM) techniques. With the nano-indentation
technique, it was possible to obtain the mechanical properties such as
hardness (H) and elastic modulus (E). The tribological characterization
allowed determining the coefficient of friction (COF) and wear rate.
Finally, the scratch and HR-C indentation methods were used to evaluate
the adhesion of the coatings to the AISI 316 substrates. A more detailed
description of the experimental techniques is presented below:
The microstructural characteristics of the coatings were evaluated
using the Raman shift spectrum, analyzed between 800 and 2000 cm− 1.
This technique is commonly used to study the microstructure of DLC
films [1–5,7]. A LabRAM Horiban Evolution spectrometer in back
scattering geometry was used to obtain each film spectrum, and the
excitation was performed with an Ar+ ion laser with a wavelength of
514 nm and power of up to 400 mW. The data acquisition time was set at
30 s, with 3 accumulations for each spectrum. The measurements were
performed under ambient temperature and humidity conditions. The
spectral shape fitting was performed using two fully symmetrical
A. Capote et al. Surface & Coatings Technology 445 (2022) 128716

Fig. 1. P&ID and schematic representation of the pulsed-DC PECVD modified system with an additional cathode.

order to avoid the influence of the silicon (100) substrate or the a-Si
Table 1
interlayer on the measurement.
Parameters used in the cleaning and deposition stages.
The internal compressive stress was determined by measuring the
Process Pressure Bias Duty Time Precursor Mass silicon (100) substrate curvature before and after the a-C:H film depo­
stages (Pa) voltage cycle (min) gases flow
sition with a KLA-Tencor stylus profilometer model AlphaStep D-500.
(-V) (%) (sccm)
The test was performed by setting the stylus speed and force at 0.1 mm/s
Ar cleaning 0.4 600 40 30 Ar 10 and 1 mg (9.8 × 10− 6 N), respectively. A total length of 5 mm was used
a-Si 0.5 800 40 30 Ar + SiH4 2+4
interlayer
for all the samples. The stress values were obtained by calculating the
Transitional P* 800 40 8 Ar + SiH4 2 + (4 radius of curvature using the least square fit method. The substrate
layer + C2H2 → 0) curvature calculated after the coating deposition can be related to the
+ 30 total stress by determining the elastic properties of the substrate mate­
a-C:H P* 800 40 60 Ar + C2H2 2 + 30
rial and by using Stoney's equation [28].
To determine the coefficient of friction and the wear rate of the DLC
Gaussian lines. The data extracted from the Raman shift spectra allow coatings, a CETR UMT-2 tribometer was used, with 4 mm diameter
the determination of the corresponding band areas and peak intensities, zirconia spheres. Before each of the tests, both the samples and the
the band position, and the full width at half maximum of the G band. The spheres were cleaned for 5 min in an ultrasonic bath with acetone. A
thickness of each film was determined from images obtained with SEM- 100 N load cell was used, and the tests were performed in accordance
FEG TESCAN model MIRA3. The film's growth rate was calculated by with ASTM G133–05, under ambient controlled conditions (temperature
dividing the thickness by the a-C:H deposition time. of 293 K and relative humidity of 40 % RH) [29]. The test parameters
The hardness and the elastic modulus of the samples were deter­ were set with an action load of 5 N, displacement speed of 10 mm/s,
mined using the nanoindentation technique. An Anton Paar UNHT3- track size of 5 mm, and test time of 10 min (300 cycles), until obtaining a
STeP E400 nanoindentation tester was used. For the test, a force was stationary coefficient of friction. The volumetric wear rate was deter­
applied with a loading rate of 6 mN/min until reaching a maximum mined by analyzing the difference between the volumes of the zirconia
value of 3 mN, which was kept constant for 5 s, thus allowing the ac­ spheres before and after the test. The volume loss was evaluated using a
commodation of the material. Subsequently, the force was removed at a Veeco/Wyko NT 1100 optical profilometer, which provides high-
rate of 6 mN/min and the diamond probe tip was removed from the resolution three-dimensional surface measurements. The wear rate
sample. The hardness and the elastic modulus were determined from the was determined by dividing the volume worn by multiplying the load by
applied force, the shape of the tip, and the depth of penetration, in the distance traveled.
accordance with the Oliver and Pharr method [27]. The penetration Two experimental techniques were used for the adhesion evaluation,
depth of the indentation was set to be <10 % of each film's thickness, in a scratch test and HR-C indentation. In the scratch test, a CETR UMT-2

3
A. Capote et al.
tribometer with a Rockwell C (HR-C) 120◦ angle diamond tip with a
radius of curvature of 200 μm was used, in accordance with ASTM
C1624–22 [30]. The load was applied progressively until reaching 60 N,
and the indenter displacement rate was set to 0.1 mm/s until it reached a
5 mm long total displacement. The point where the first crack occurred
was labeled critical load Lc1, and the value of the load where substrate
exposure was observed was labeled critical load Lc2. The second tech­
nique used for the adhesion evaluation was based on the VDI 3198
indentation test [31]. The HR-C indentation test was performed in a
Reicherter Briviskop BVR 187.5H hardness tester, using a conical dia­
mond tip and a load of 1471 N. The test was performed on the AISI 316
coated surface, producing a notable plastic deformation in the substrate.
Analysis of SEM/FEG micrographs of the produced failure, when
compared with the image standard proposed in the VDI 3198 standard,
is useful for classifying it as acceptable or unacceptable coating adhesion
[31].
3. Results and discussion
3.1. Microstructure of the a-C:H films
In the Raman spectra of DLC films, changes in the position, intensity,
and width of the D and G bands can be related to possible microstruc­
tural variations of the coatings [32]. In the Gaussian fitting of the Raman
shift spectrum, the graphite band (G), usually with a peak position
around 1550 cm− 1, is related to the vibration modes of the atom bonds
with sp2 hybridization in the aromatic rings or the olefin chains [7,33].
On the other hand, the disorder band (D), usually with a peak position
around 1350 cm− 1, is related to the interaction forces or breathing
modes of the aromatic rings present in the cluster agglomerations
[7,33].
The Raman shift spectra of the films showed that there is no signif­
icant difference in the spectral profiles of the samples deposited at
different pressures when other deposition parameters are kept constant.
The typical Raman spectra of films grown with internal pressures be­
tween 0.1 and 1.3 Pa are shown in Fig. 2. The Raman spectra analyzed
for all the films showed a position of the D and G band centered around
1380 cm− 1 and 1555 cm− 1, respectively. In comparison with the normal
peak positions for DLC deposited using the conventional PECVD tech­
nique, in this modified system it's possible to identify that position of
both the D and the G bands are shifted, mainly attributable to the
incorporation of an additional cathode [12]. In this novel technique, the
confinement of ions and electrons increases the plasma density, thus
Fig. 2. Raman shift spectrum for the a-C:H film deposited on Si (100) at 0.4 Pa.
The Gaussian fitting lines show the D and G bands.
4
Surface & Coatings Technology 445 (2022) 128716
altering the microstructural characteristics of DLC films. Several expla­
nations have been suggested for the displacement of the D and G bands;
these include changes in the size of the clusters, their atomic distribu­
tion, the presence of internal compressive stress, and the chemical na­
ture of the bonding [5,33]. A phase transformation towards denser
atomic packing structure and some types of chemical recombination can
induce tensile stress [34–36]. This may explain the ~25 cm− 1 down­
shifted G band of the a-C:H films obtained, in comparison with the non-
stressed Raman shift G peak (at 1580 cm− 1) [34,36].
The Gaussian fitting of each spectrum allowed identifying the in­
tensity and position of the D and G bands, as well as the full width at half
maximum of the G band peak (FWHMG). In the Raman spectra of DLC
films, changes in those parameters are related to possible microstruc­
tural variations of the coatings [32]. The intensity ratio for the D and G
bands (ID/IG), the G band peak position (ωG), and the FWHM of the G
band (ΓG), obtained from the fitted parameters of DLC films growth with
variable deposition pressure, are plotted in Fig. 3. These results are
typical values for these parameters in high-quality a-C:H, and they are
similar to results obtained in previous studies [8,10,20,34]. In disor­
dered a-C:H materials, it is known that the D band is affected by different
carbon structures and is formed whenever no C with sp3 hybridization
sites exist, confirming that with Raman spectroscopy it is generally not
possible to determine the sp3/sp2 concentration ratio or the detailed
microstructural organization [34,35].
The ID/IG ratio shows a slight increase at lower deposition pressures.
In amorphous carbon films, the ID/IG ratio is usually a parameter qual­
itatively related to the phase size with sp2 hybridization organized into
aromatic rings, while the FWHMG value is mainly sensitive to structural
bond distortions [5]. The increase of the band's intensity ratio, together
with the shift of the G band's position towards higher wave numbers,
accompanied by a reduction in the FWHM of the G band, is usually
interpreted in terms of an increase of the sp2 clusters' dominion, either in
number or in size [33,34].
On the other hand, the FWHMG values showed a tendency to remain
Fig. 3. ID/IG intensity ratio, G peak position (ωG) and FWMHG (ΓG) for the
films deposited on Si (100) as a function of the pressure.
A. Capote et al.
constant for all pressures, with a value of around 165 cm− 1. Considering
the observed stability of the FWHMG value, it can be suggested that
increasing the internal pressure in the range evaluated is not associated
with structural disorder formation in the deposited DLC films' structures.
However, in Raman spectra the stress shift must be considered for the
correct assignment of the peaks [36]. Also, the results must be com­
plemented with other solid-state characterization techniques in order to
provide accurate interpretation of the material's structure, atomic
bonding, and network organization [35].
The modified PECVD technique with an additional cathode stands
out because of the possibility of obtaining DLC films with an improved
growth rate at low deposition pressure. The deposition rate was
measured by calculating the average thickness of the coatings deposited
on silicon (100). The cross-section micrographs of each film, such as the
one shown in Fig. 4, allowed differentiating the stages of the deposition
process and their respective thicknesses. Additionally, it was possible to
identify that the morphology of the DLC film growth was apparently a
dense, slightly columnar structure, a characteristic growth form for this
type of coating [37–39]. The growth rate of the a-C:H films as a function
of the internal deposition pressure is shown in Fig. 5. A relatively high
growth rate was obtained (>17 nm/min), and a linear correlation with
the internal pressure was observed. At low pressures (up to 0.1 Pa), the
modified PECVD system allowed growing DLC films with relatively
higher deposition rates (about 1 μm/h), whereas a conventional PECVD
system is not suitable for obtaining DLC films at similar pressures due to
the high plasma instability. One possible explanation is that when using
a conventional system, lower deposition pressure involves a lower
probability of collision between electrons and molecules, thus reducing
the level of dissociation and ionization of the precursor gases. Despite
that, the addition of an extra cathode increases the density of highly
energetic species in the plasma phase (electrons, C+ ions, and radicals),
due to the partial confinement [12]. Therefore, in this near collision less
scenario, the lowest deposition pressures where it is possible to achieve
plasma stability allow increasing the ions' average energy while nar­
rowing the ions' energy distribution.
3.2. Mechanical and tribological properties of the a-C:H films
Some mechanical properties, such as hardness (H) and elastic
modulus (E), can be modified by controlling the deposition parameters
[39,40]. In general, the plastic index H/E ratio serves as a parameter for
identifying the mechanical behavior of this type of material in wear
control [40]. While low H/E ratios usually indicate high resistance to
Fig. 4. SEM micrograph 50 kx of the cross section for the a-C:H film deposited
on Si (100) at 0.5 Pa.
5
Surface & Coatings Technology 445 (2022) 128716
Fig. 5. Growth rate of the a-C:H film deposited on Si (100) as a function of the
deposition pressure.
elastic deformation, high H/E values indicate high wear resistance.
Depending on the application of the DLC coatings, it is necessary to
guarantee a high degree of hardness in order to improve the tribological
properties of the films and an adequate adhesion of the films to the
deformations produced. A modified H/f.E (coefficient of friction, f)
criterion can be used as a qualitative way to predict superior anti-wear
results of hard carbon coatings [34]. Variations in the surface micro-
roughness and the coatings' surface chemistry have an effect on the
coefficient of friction. The coating's roughness can be improved by
reducing the surface diffusion and recrystallization effects during the
film's nucleation and growth, when ions and radicals are able to develop
stronger atomic interlinking bonds with the film's surface, and when
lower deposition temperature has been achieved [34,35]. Lower local
temperature at the film's atomic-scale surface may be achieved by using
a pulsed deposition system, where the heat loss is more efficient and
there is a reduced probability of degrading the deposited carbon mate­
rial [34]. Some transformations from diamond-like to graphite-like can
be leaded due to friction heat; also, film oxidation and surface passiv­
ation should be considered in order to reach a more detailed wear
behavior analysis. Moreover, the total compressive stress of a-C:H films
is highly relevant, affecting the coating's adherence and anti-wear
behavior.
In the nanoindentation test, the penetration depth was monitored
during the loading and unloading stages. From the load-depth curves, as
shown in Fig. 6, it is possible to quantify the contact area at the
maximum load by using the contact depth (hc) and the material's contact
stiffness by using the initial unloading curve tangential slope (S) [27].
From the indenter geometry and the projected contact area, the hard­
ness, elastic modulus, and plastic index values for the films' growth at
different deposition pressures were obtained and are shown in Table 2.
The films reached their maximum H and E values at the lowest pressure,
27.8 ± 1.2 GPa and 207.3 ± 5.2 GPa, respectively. The hardness and the
elastic modulus of the DLC coatings exhibited a tendency to decrease
with an increase in the deposition pressure. It can be inferred that the
inferior mechanical properties obtained for films deposited at 0.7 Pa or
higher pressures is related to the amorphization trajectory described in
the Raman microstructure characterization. Also, an explanation is that
at higher pressures the neutral species in the plasma phase (radicals and
intact molecules) make an important contribution to the films' mass
growth. This phenomenon is governed by the chemical reactivity of the
radicals and molecules at the C–H or C–C sites [14,15,41]. The ob­
tained DLC films have a significantly higher degree of hardness than the
uncoated AISI 316 stainless steel substrates (~1.5 GPa), reinforcing the
relevance of a-C:H as a protective coating for metallic surfaces. Also, it
A. Capote et al. Surface & Coatings Technology 445 (2022) 128716

Fig. 6. Penetration curves obtained from nanoindentation tests for a-C:H films
deposited on Si (100).

Table 2
Hardness (H), elastic modulus (E), plastic index parameter (H/E) and indenta­
tion depth of the DLC films deposited on Si (100) as a function of the deposition
pressure.
Pressure H (GPa) E (GPa) H/E Indentation depth
(Pa) (nm)

0.1 27.8 ± 207.3 ± 0.13 ± 92.8 ± 1.5 Fig. 7. Residual compressive stress and average roughness for the a-C:H films
1.2 5.2 0.01
deposited on Si (100) as a function of the pressure.
0.3 23.3 ± 195.3 ± 0.12 ± 94.4 ± 0.8
1.1 6.6 0.01
0.4 22.9 ± 171.6 ± 0.13 ± 101.5 ± 1.0 recrystallization of the graphite [16,34,35].
0.8 4.4 0.01 The coefficient of friction (COF) experienced some transitions
0.5 22.8 ± 179.4 0.13 ± 99.3 ± 1.6
throughout the tribological test. In general, these transitions are natural
±
1.0 4.6 0.01
0.7 15.5 ± 142.5 ± 0.11 ± 116.0 ± 3.7 or induced [43]. These transitions may involve changes in surface
1.3 9.0 0.01 roughness as well as variations in the surface composition or the for­
1.3 15.7 ± 128.4 ± 0.12 ± 124.8 ± 14.0 mation of a third body. Fig. 8 shows the behavior of the coefficient of
1.4 9.3 0.01
friction of the a-C:H films obtained at 0.1, 0.5, and 1.3 Pa, respectively.
For the film's growth at the lowest pressure, it is possible to identify a
was possible to identify high H/E ratios for the DLC coatings. The in­ running-in stage followed by a steady-state friction. This frictional
fluence of the internal pressure indicates that high H/E ratio, up to 0.13 behavior may be described as a case of boundary lubrication. An initial
± 0.01, could be reached in coatings obtained under 0.5 Pa. Therefore, it increase in the COF value due to the contact surface's asperities is
is possible to suggest that the a-C:H films grown at lower pressures tend
to have better wear resistance characteristics.
Determining the total compressive stress is important for improving
the practical adherence of the films, but it should also be considered in
order to achieve a more accurate understanding of the material char­
acterization. Whereas interfacial stress is related to a-C:H film's atomic
mismatch with the a-Si interface, the intrinsic stress and the coating's
thickness make a major contribution to high stress levels [34,35]. By
using the Pauleau formula [42], the intrinsic stress of the films obtained
at the highest pressure is expected to be up to 3 times higher than the
film's growth at 0.1 Pa. The total compressive stress and the surface
roughness of the a-C:H films as a function of the deposition pressure is
shown in Fig. 7. Relatively low compressive stress values, between 0.7
± 0.1 GPa and 1.8 ± 0.2 GPa, were calculated for the studied films. As
expected, higher stress values were observed in the coatings with greater
thickness. The average surface roughness of the a-C:H films deposited on
Si (100) showed that with higher deposition pressures, the roughness
tends to increase. Average surface roughness values between 4.1 ± 0.1
nm and 12.3 ± 1.2 nm were observed (see Fig. 7). The increase of sur­
face roughness could be associated with the larger number of energetic
positive ions impinging on the surface, which can lead to a preferential Fig. 8. Frictional behavior of the a-C:H film deposited on AISI 316 as a function
surface sputtering, higher surface temperature, and the effects of stress of the time.

6
A. Capote et al.
gradually reduced as a result of the smoothening of the surfaces, mainly
due to wear and plastic deformation [43]. For the film's growth at 0.5
and 1.3 Pa, a different frictional behavior was observed. These curve
shapes are usually identified in hard coatings on ceramics. This behavior
is related to roughness changes followed by debris layer formation
[44,45]. The coefficient of friction and the wear rate of the obtained
films as a function of the deposition pressure are shown in Fig. 9. Low
COF values, between 0.087 ± 0.002 and 0.122 ± 0.002, were measured
for the coatings. These results showed that samples with higher values of
average surface roughness consistently exhibited the highest COF.
However, the coefficient of friction of the deposited films is relatively
low and suggests the major advantage of using DLC coatings as solid
lubricants when compared to the high coefficient of friction (approx.
0.6) of polished AISI 316 stainless steel substrates.
A wear track was formed on the DLC coatings' surface due to the
typical abrasive mechanism at relatively high load conditions [39,46].
Three-body abrasive wear can be verified from the presence of a transfer
layer observed in the contact area on the zirconia sphere's surface.
Larger zirconia volume loss and wear debris were noticed for the films'
growth at internal pressures above 0.5 Pa. The highest wear rate was
observed for the film obtained at the highest pressure, and the volu­
metric wear was (20.8 ± 1.4) x10− 8 mm3/Nm. This increased wear can
be explained by the film's lower hardness and lower H/E ratio, in
addition to the increased COF, which could lead to an insufficient
transfer layer formation at the DLC coating and zirconia ball interface.
By contrast, the hardest DLC film exhibited lower missing net volume
and more shallow wear scar surface morphology. The lowest wear rate
was observed for the film grown at 0.1 Pa: the volumetric material loss
was estimated at around (4.3 ± 1.3) x10− 8 mm3/Nm. Thus it was
possible to determine that the coatings with higher hardness values
exhibited lower volumetric wear rates. Additionally, the H/E ratio, or
plastic index, can be used as a comparative parameter between DLC
protective coatings in order to classify their resistance to wear.
3.3. Adherence of the a-C:H films
Obtaining adherent DLC films on metallic surfaces is influenced by
several variables of the deposition process, such as the presence and
strength of compressive residual stresses, the film's microstructure
composition, the interlayer bonding, and the physical and chemical
properties of the substrate, such as roughness and type of material.
Extensive research has been carried out by DIMARE-INPE (Brazil) group
[9–13,20,23–25,47]. In previous investigations, DLC deposition on
metallic substrates without the incorporation of an a-Si interlayer
Fig. 9. Coefficient of friction (●) and wear rate (□) for the a-C:H films
deposited on AISI 316 as functions of the pressure.
7
Surface & Coatings Technology 445 (2022) 128716
completely delaminated due to the considerably higher total compres­
sive stress of the film, approximately − 3.5 GPa [10]. To overcome the
presence of high residual stress on the deposited DLC films, a thin
amorphous silicon interlayer of about 250 nm in thickness has consis­
tently been used as an interface between the a-C:H layer and the sub­
strate surface. Strong chemical bonding between the Si 2p and C 1 s is
probably responsible for decreasing the film's stress and improving the
adherence of the a-C:H film to the a-Si interlayer [23].
A semi-quantitative measure of adherence of the DLC films was
evaluated with a scratch test, the determination of the critical loads was
performed while considering the evolution of the coefficient of friction,
the received signal measured by an acoustic emission sensor and the
breakpoints of the track's micrographs. The critical load values (Lc1 and
Lc2) are shown in Fig. 10. The coatings obtained with pressures lower
than 0.5 Pa have critical loads Lc1 and Lc2 >6.4 ± 1.2 N and 19.7 ± 1.4
N, respectively. By comparison, the films deposited at higher pressures
have critical loads lower than 3.0 ± 1.3 N and 2.7 ± 1.1 N. These values,
Lc1 and Lc2, were low in comparison with the values of the other samples
and were consecutive among themselves; once reaching critical load Lc1,
critical load Lc2 was immediately recorded. The lower critical load
values were observed in the samples obtained at pressures above 0.5 Pa
were expected, due to the higher total compressive stress of the films, up
to 2.6 times higher when compared with the lowest deposition pressure.
It has previously been shown that the deposition of DLC films via the
modified PECVD technique with an additional cathode allows better
adhesion of the films to the substrate, due to the intense ionic action in a
near collision less regime [13]. In this deposition technique measured
total compressive stress levels were relatively lower than the total stress
(≥ − 2.5 GPa) achieved using the r.f. PECVD deposition technique
[23,25]. Thus, this novel technique allows the growth of films at low
pressures, increasing the mean free path, and as a consequence, a greater
ionic penetration depth is reached. In addition, low internal pressures
favor the reduction of residual stresses that end up affecting the adhe­
sion of the films to metallic substrates. The delamination of DLC films
when subjected to mechanical loads generally implies that the coatings
are not suitable for some industrial applications. The VDI 3198 inden­
tation test was used to qualitatively control the adhesion of the depos­
ited coatings [30]. The HR-C macro-indentations performed on the
coated substrates are shown in Fig. 11. When compared to the VDI 3198
standard, the coatings obtained at pressures lower than 0.5 Pa exhibited
an acceptable pattern of failure and therefore an adequate interfacial
adhesion between the films and the substrates, possibly due to the much
lower measured total compressive stress of the films. However, the
coatings grown at higher pressures exhibited failure patterns that
Fig. 10. Critical load values Lc1 and Lc2 for the a-C:H films deposited on AISI
316 as a function of the pressure.
A. Capote et al.
Fig. 11. SEM micrographs of HR-C indentation test for the a-C:H films deposited on AISI 316 at variable pressure.
indicate low interfacial adhesion. The qualitative control results are
congruent with the scratch test results, due to the decrease in the value
of critical loads for the coatings deposited at pressures >0.7 Pa. Thus,
suggesting a poor adhesion of the coatings to the substrate when sub­
jected to a force or work in the coated substrate surfaces. Thick DLC
coatings (>2.5 μm) with significantly lower stress (about 0.6 GPa) and
good adherence were obtained previously, using a multilayer structure
adding thin a-Si interlayers between the a-C:H layers, where each DLC
8
Surface & Coatings Technology 445 (2022) 128716
layer was grown with approximately 500 nm in thickness [20].
4. Conclusions
The influence of low deposition pressure on the microstructural,
mechanical, and tribological properties and the adherence of a-C:H
coatings have not previously been systematically studied. By employing
a modified pulsed-DC PECVD technique with an additional cathode, the
A. Capote et al.
characterization of some a-C:H films' properties was reported. The re­
sults for coatings grown between 0.1 Pa and 1.3 Pa suggest that this
novel system might be a good alternative for the deposition of a-C:H
films for mechanical and tribological applications, with relatively simple
reactor equipment, lower process operation cost, and easy scaling up.
However, it should be taken into consideration that the characteristics of
each reactor system, precursor atomic ratios, and level of purity of the
precursor gas mixtures, as well as other controllable or non-controllable
deposition parameters, exert a major influence on a-C:H characteriza­
tion results, especially when compared to other conditions or deposition
techniques.
The study of the microstructural composition suggests a similarity in
the Raman spectra for all the films, with slight variations in the ID/IG
ratio, while the G band's position and FWHMG remain constant. Deter­
mining the influence of the internal pressure on the growth rate makes it
possible to predict the thickness of coatings obtained under equivalent
conditions. The characterization of the mechanical properties indicates
that at low pressure it is possible to obtain a-C:H films with high hard­
ness and elastic modulus, up to 28 GPa and 207 GPa, respectively. The
effect of the deposition pressure on the films' total compressive stress
was observed by measuring the curvature of the deposited a-C:H coat­
ings; at lower deposition pressures, reduced stress levels were achieved.
The characterization of the total stress of a-C:H films is relevant to the
understanding of the practical adherence and tribological behavior of
the coating material. At all studied deposition pressures, low coefficients
of friction and wear rates were achieved, but the films grown at pres­
sures lower than 0.7 Pa stand out, due to their greater hardness and
lower COF values. By correlating the plastic index ratios and the coef­
ficient of friction results, it is possible to identify the influence of these a-
C:H films' properties on superior anti-wear behavior. Finally, the inter­
facial adhesion of the films was determined to be acceptable, except for
the films obtained at higher pressures, due to the lower critical loads and
the unacceptable delamination of the films.
CRediT authorship contribution statement
A. Capote, and V.J. Trava-Airoldi: Conception and design of study.
A. Capote: Acquisition of data:
A. Capote, G. Capote, and V.J. Trava-Airoldi: Analysis and/or
interpretation of data.
A. Capote and G. Capote: Drafting the manuscript.
A. Capote, G. Capote, E.J. Corat and V.J. Trava-Airoldi: Revising the
manuscript critically for important intellectual content.
Declaration of competing interest
The authors declare the following financial interests/personal re­
lationships which may be considered as potential competing interests:
Ariel Capote reports financial support was provided by Conselho
Nacional de Desenvolvimento Científico e Tecnológico (CNPq).
Data availability
Data will be made available on request.
Acknowledgments
The authors wish to thank the Fundação de Amparo à Pesquisa do
Estado de São Paulo – FAPESP (grant numbers 2019/18572-7 and 2012/
15857-1), Conselho Nacional de Desenvolvimento Científico e Tec­
nológico – CNPq (grant number 132884/2020-8), Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior – CAPES, and Ph.D. Ca­
rina Barros Mello (INPE-Brazil) for the experimental support.
9
Surface & Coatings Technology 445 (2022) 128716
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