Applied Surface Science 303 (2014) 187–195

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Applied Surface Science

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

DLC coating on stainless steel by pulsed methane discharge in

repetitive plasma focus
M. Hassan a,c,∗ , A. Qayyum b , S. Ahmad b , S. Mahmood c,d , M. Shafiq a , M. Zakaullah a ,
P. Lee c , R.S. Rawat c
a
Department of Physics, Quaid-i-Azam University, 45320 Islamabad, Pakistan
b
National Tokamak Fusion Program, 3329 Islamabad, Pakistan
c
Natural Sciences and Science Education, National Institute of Education, Nanyang Technological University, BLK7, 1 Nanyang Walk, Singapore 637616,
Singapore
d
Department of Physics, University of Karachi, 75270 Karachi, Pakistan

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

Article history: Amorphous hydrogenated carbon (a-C:H)/diamond-like carbon (DLC) coatings have been achieved on
Received 8 June 2013 AISI 304 stainless steel (SS) substrates by employing energetic ions emitted from a repetitive plasma
Received in revised form 21 February 2014 focus operated in CH4 discharge. The Raman spectroscopy of the coatings exhibits the evolution of a-
Accepted 24 February 2014
C:H/DLC coatings with clearly observed D and G peaks centered about 1320–1360 and 1560–1620 cm−1
Available online 12 March 2014
respectively. The diamond character of the coatings is influenced by the ion flux and repetition rate of the
focus device. The repetitive discharge mode of plasma focus has led to the formation of a-C:H/DLC coatings
PACS:
in short duration of time. The coatings transform from a-C to a-C:H depending upon substrate angular
52.59Hq
52.77Fv
position. X-ray diffraction (XRD) analysis confirms the formation of DLC coating owing to stress-induced
61.05cp restructuring in SS. The estimated crystallite size is found to be ∼40–50 nm. Field emission scanning
electron micrographs exhibit a layered granular surface morphology of the coatings. The Vickers surface
Keywords: hardness of the DLC coated SS samples has been significantly improved.
DLC © 2014 Elsevier B.V. All rights reserved.
DPF
XRD
SEM
Raman spectroscopy

1. Introduction popularity because of their superior physical properties such as

high hardness, high strength, and better stability at high temper-
Carbon can exist in three different chemical states, involving ature, high optical transparency, high thermal conductivity, high
sp3 , sp2 and sp1 chemical co-ordination. Eventually, a variety of dielectric strength, high chemical inertness and low coefficient of
structures can be resulted, which may also contain other chemical friction. Eventually, DLC coatings find their suggested use in the
elements. Mainly, there are two types of diamond-like structures; field of tribology (reduction of friction, wear, erosion, cavitation),
identified explicitly as hydrogenated amorphous carbon (a-C:H) bioengineering, both passive and active electronics elements and
or diamond-like hydrocarbons and non-hydrogenated amorphous optics.
carbon (a-C) or diamond-like carbon (DLC). Such a-C:H and a- A wide range of materials can be opted as a substrate for DLC
C coatings have received much scientific interest owing to their coatings. The choice of AISI 304 stainless steel (SS) having high
useful mechanical properties. Raman features of a-C:H coatings strength, excellent corrosion resistance and excellent formabil-
deposited at room temperature were discussed by Schwan et al. ity makes it useful for various applications. Typical uses include
[1]. They showed that small clusters of condensed benzene rings architectural moldings and frames, kitchen equipment, as well as
in carbon films can be explained in the observed Raman scatter- chemical, textile, paper and chemical industry processing equip-
ing. Like diamond, the DLC coatings have also attained remarkable ment. AISI 304 stainless steel has been deposited with DLC coatings
by physical vapor deposition and investigated for corrosion resis-
tance [2]. Its tribological performance has been investigated by
∗ Corresponding author at: Department of Physics, Quaid-i-Azam University, duplex surface treatment i.e. plasma electrolytic nitrocarburising
45320 Islamabad, Pakistan. Tel.: +92 3004237931. and plasma-immersion ion-assisted deposition of DLC coatings
E-mail addresses: [email protected], [email protected] (M. Hassan). [3,4] and sputter deposition [5].

http://dx.doi.org/10.1016/j.apsusc.2014.02.142
0169-4332/© 2014 Elsevier B.V. All rights reserved.
188 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195

Table 1
Technical parameters of the repetitive plasma focus (NX2) device used for DLC coating on SS.

Parameter Specification Parameter Specification

Capacitance, C0 27.6 ␮F (0.6 ␮F × 46) Inductance of circuit, L0 26 nH

Operating charging voltage, V0 13.5 kV Impedance, Z0 (L0 /C0 )1/2 = 31 m
Maximum charging voltage, V 15 kV Maximum current, I0 430 kA
Maximum stored energy, E 3.1 kJ T/4 time of short circuit, t 1.33 ␮s
Operating repetition rate, f 0.5 and 1.0 Hz Anode (copper) length, la 45 mm
Anode diameter, a 31 mm

The amorphous nature of DLC coatings allows the uniform of 2.5 mbar. The NX2 device employs a Cu anode having engraved
coverage of surface. A variety of techniques like chemical vapor tip in order to reduce the impurities introduced into plasma [11].
deposition (CVD) [6], pulsed laser ablation [7], cathodic arc plasma When the electrical energy stored in the capacitor bank (four mod-
deposition [8], pulsed electrode surfacing [9] and sputtering by ion ules CB1, . . ., CB4) is transferred to the electrode system by low
beam [10] were successfully applied to produce these coatings. inductance pseudo-spark gap (PSG) switches, the gas breakdown
Recently, the dense plasma focus (DPF) has been employed for occurs initially across the surface of the insulator sleeve separating
the development of surface properties of various materials. The the anode and the cathode. The breakdown, under the influence of
DPF is a simple and low cost pulsed coaxial plasma accelerator Lorentz forces, proceeds on to form uniform, axis symmetrical cur-
that produces a short lived plasma pinch of very high densities rent sheath in inverse pinch phase and is then accelerated down the
(∼1025 to 1026 m−3 ) and high temperatures (1–2 keV). The DPF is a anode axis during axial rundown phase. Upon reaching the top of
bright source of multi-radiations such as highly energetic (25 keV to the anode, the current sheath collapses radially inward resulting in
8 MeV) high fluence ions, relativistic electrons, X-rays and neutrons the formation of hot dense pinched plasma at the top of the anode
[11–15]. The ion beam is mainly emitted in the forward direction during the final focus phase. The plasma temperature is sufficiently
(with respect to the electrode axis), within a cone with an aper- high to cause complete ionization of the working gas. CH4 , being the
ture angle ranging from 30◦ to 70◦ depending on their energy [16]. working gas, supplies ions in almost all ionization states [11]. The
These highly energetic ions have been used to grow crystalline TiO2 formation of hot dense plasma is followed by the onset of sausage
[17], to induce crystallization in amorphous lead zirconate titanate (m = 0) instability. This instability enhances the induced electric
(PZT) films [18], to change the orientation of CdI2 films [19], to field locally, and hence breaks the focus plasma column [27]. This
deposit nanocrystalline multiphase titanium oxycarbide thin films leads to the acceleration of gaseous ions with very high energies
on Ti [20], to deposit TiN films on Ti [7], on Zr [21], on AISI-304 toward the top of the chamber. The key plasma charged particles
[22], to modify the surface of austenitic SS [23], and to improve the (energetic ions and electrons) and radiation (EUV, X-rays, neutrons,
wear behavior of SS and Ti by nitrogen implantation [24]. Energetic etc.) characteristics for plasma focus devices are well established
ions emitted from low energy DPF (PF II) device have also been through various experimental and simulation studies. The energies
employed to deposit well-adhered TiN coatings on AISI 1010 and of instability-accelerated ions, which mostly move towards the top
AISI 304 SS due to ion-induced strong heating of superficial layer of the anode, are in the range of tens of keV to a few MeV [28,29]. It is
of SS and diffusion of impinging ions [25]. The use of DPF device as also a well-established fact that the dimensions of coaxial electrode
an ion implanter has been found to be feasible that could perform assembly, electrical energy stored in the capacitor bank, peak dis-
nitriding in short time intervals. Heating rate of ∼15 K ns−1 , tem- charge current flowing through the plasmas, and the operating gas
perature gradients of 1500 K mm−1 and peak temperatures near the type do not affect many of the key characteristics such as plasma
melting point played an important role in the surface modification density, plasma temperature, current sheath speeds, radiation and
process. ion energy spectra etc., of the optimized DPF devices indicating the
The use of plasma focus for materials processing has demon- unique universality in the DPF devices [26]. Hence for the methane
strated its interesting features of high deposition rates and good filled NX2 DPF device operation the energy of the carbon and hydro-
adhesion owing to its wide energy spectrum of radiations [16–18]. gen ions will also be in the range of few tens of keV to a few MeV.
Various features and characteristics of plasma focus device that More detailed information about ion beam characteristics of DPF
makes it a unique device for applications in materials processing devices have recently been estimated and reported by Lee and Saw
and deposition are provided in detail in a recent review paper by [30,31].
Rawat [26]. Further details of NX2 DPF operation and the preliminary diag-
The aim of the present work is to deposit DLC coatings on SS nostics can be found elsewhere [13]. The energetic ions emitted
using ions of a repetitive DPF device designated as Nanyang X-ray from the focus plasma are utilized for the formation of DLC coatings
source-2 or NX2 plasma focus device [13] for two different focus on AISI 304 samples. The important parameters are ion energy, ion
shot repetition rates as a function of angular position of deposition flux which is controlled by distance or angle of deposition, oper-
substrate with respect of anode axis. Raman spectroscopy, X-ray ating voltage, filling pressure, shot to shot reproducibility and the
diffraction (XRD), and energy dispersive X-ray spectroscopy (EDS) repetition rate of the device that may strongly influence the physi-
are used to investigate sp2 and sp3 bonding, structural and elemen- cal characteristics of the coating at a particular deposition position.
tal changes respectively, whereas field emission scanning electron The NX2 device has been operated under optimum discharge condi-
microscopy (FESEM) is used to study the surface morphology of the tions for CH4 plasma. The chamber pressure of NX2 is highly stable
DLC coatings. and hence the shot to shot reproducibility of this device, monitored
and established by intense voltage peak in high voltage probe sig-
2. Experimental setup nal and sharp dip in current derivative Rogowski coil signal [13], is
excellent.
For the present experiment, the DPF device is operated in auto DLC films were deposited on highly polished
trigger mode with repetition rates of 0.5 and 1.0 Hz. The technical 15 mm × 15 mm × 1 mm stainless steel-304 substrates with
parameters of the device are given in Table 1. The discharge cham- surface roughness average of approximately 30 Å as measured by
ber is evacuated down to 10−4 mbar using turbo molecular pump, TENCOR P-10 Surface Profiler. The SS samples were ultrasonically
and is then filled with CH4 as working gas at an optimum pressure cleaned sequentially with de-ionized water, acetone and ethanol
 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195 189

Fig. 1. Schematic diagram of repetitive plasma focus used for DLC coatings. Pseudo-spark switches PSG1 to PSG4 facilitate minimum inductance switching of current in
repetitive mode discharge. AISI 304 samples are mounted in the processing chamber at ambient temperature.

for 15 min each at 30 ◦ C. Total three (03) samples were coated for (0.5 and 1.0 Hz). All depositions were carried out using 30 focus
a particular repetition rate. The samples were mounted at axial shots for these repetition rates of 0.5 and 1.0 Hz. Raman spec-
distance of 9 cm from the anode tip at different angular positions troscopy analysis of deposited carbon coatings is performed using
such as at 0◦ , 10◦ and 20◦ with respect to the anode axis as shown a Renishaw MicroRaman spectrometer equipped with an argon
in Fig. 1. The estimated area of the nitride zone viewed from the top ion laser that uses excitation wavelength of 514 nm. The spec-
of the conical cross-section is ∼50 cm2 . Noticeably, the deposition trometer has spectral resolution of 1 cm−1 . The Raman spectra are
of films such as TiN [12,22] along the anode axis at lower axial acquired over the range of 10–2000 cm−1 in the back scattering
distance has been reported with significant surface damage by the geometry by measuring the inelastically scattered light from the
last treatment shot because of the maximum energy and flux of sample. By fitting the peaks with Gaussian distribution, Raman
ions along the axis. Eventually, the deposition of these films was spectra are also used to estimate the sp2 to sp3 ratio that deter-
conducted at different angular positions (referred as 0◦ , 10◦ and mines the diamond character in the deposited layer. XRD analysis
20◦ ) with respect to the anode axis. is used to investigate the possible changes in the microstructure
The conditions for DLC coatings (substrate position, no. of shots) of SS 304 samples. SEM along with EDS is employed to study the
in the present work have been selected based on plenty of work surface morphology and elemental composition of the coatings.
conducted [20–22]. Since the DPF has well established ion pro- SEM micrographs were acquired at a tube voltage of 5 kV, electron
file (flux and energy distribution) in the conical geometry [16], current of 10 ␮A and working distance varying from 3 to 8 mm.
the ion flux reduction with increasing conical angle affects the EDS analysis was performed at a tube voltage of 10 kV, electron
quality of the DLC coatings. The goal was to select the optimum current of 20 ␮A and working distance of 15 mm. Wilson Wolpert
angular position when deposited for two different repetition rates 401MVA Vickers micro-hardness tester is employed to determine
190 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195

show the emergence of two broad bands, centered at around

1330–1360 cm−1 (D band) and 1560–1620 cm−1 (G band). The
occurrence of D and G bands explicitly reports the presence of DLC
coatings on the SS 304 substrates. The intensity and broadening
of D and G bands enlighten the strength of sp2 and sp3 bonds. The
broadening of bands can be assigned to the second order scattering
or some disorder-induced vibrational mode [34]. The incorporation
of gaseous impurities as well as those from electrodes, left unsput-
tered during coatings, leads to the broadening of such bands. The
emergence of D and G Raman peaks for all samples points to the
successful deposition of DLC coatings on SS substrates for 30 focus
shot depositions at all three angular positions for both repetition
rate operations. The quality of the DLC coatings, in terms of peak
intensity ratio, depends on the spatial distribution of ion beams.
Since plasma focus has been well investigated for the axial [12]
and angular distribution of ion beams [35], the depositions done
at 10◦ and 20◦ angular positions provides sufficient ion energy and
flux to establish sp2 and sp3 bonds characterized by D and G bands.
The advantage of the repetitive NX2 device over a single shot
device is its higher repetitive rate performance unlike a conven-
tional single shot DPF device usually operated in manual trigger
mode [36] with shot interval of about 1–2 min. Substantial thick-
ness (about one micron or so) of coatings can be achieved in a
short duration while operating the DPF device in repetitive mode.
However, in the repetitive mode, energetic ions bombardment may
increase the substrate temperature if no cooling is arranged.
The plasma focus device is pulsed plasma device and hence
the substrate temperature variation upon its exposure to energetic
pulsed ion beams is also a transient phenomenon with extremely
high temperature rise rate (∼40 K ns−1 ) followed by rapid quench-
ing [37]. So if the device is used in single shot mode with average
shot interval of 1 min or so, then rise in average substrate tem-
perature will be negligible even though there is intense transient
heating. However, for repetitive operation the average substrate
temperature was not negligible as estimated by Rawat et al. [17].
For 2.0 Hz repetition rate, they reported [17] the increase in aver-
age substrate temperature from room temperature of 295 K to
about 310 K for 100 NX2 DPF device shots; while for low repeti-
tion rate of 0.2 Hz the average substrate temperature increase was
only about 1–2 K. In the present experiment, two repetition rates
0.5 Hz and 1.0 Hz achieved the DLC coatings respectively in 60 and
30 s for 30 focus shots. The DLC coatings deposited for both rates
show distinct compositional and morphological profile for partic-
ular angular positions.
For 0.5 Hz rate (Fig. 2a), the D and G peaks are less intense due to
the slower rate of ion energy/flux imparted at substrates at this rate.
Fig. 2. Raman spectra of the DLC coatings deposited at different angular positions A high content of sp3 carbon bonding in the DLC films is believed
(0◦ , 10◦ and 20◦ ) for repetition rates of (a) 0.5 Hz and (b) 1.0 Hz.
to be responsible for the weak feature of the Raman peaks, because
the Raman phonon line is more sensitive to the sp2 carbon bonding.
the micro-hardness as a function of indentation depth in the DLC However, for 1.0 Hz DPF operation rate (Fig. 2b), the temperature
coatings. rise of few K due to faster deposition rate seems to assist the growth
of DLC coatings with enhanced Raman D and G peaks.
3. Results and discussion Rapid cooling of the sample surface between consecutive shots
as discussed quantitatively by many authors [12,23,24] renders the
3.1. Raman spectroscopy surface less energetic. Increasing the shot to shot repetition rate
raises the temperature of the substrate in the near surface region
Raman spectroscopy is a standard non-destructive tool for the to few K, which further helps in formation of DLC deposition. Qual-
characterization of crystalline, nanocrystalline and amorphous car- itatively, the intensity of D and G bands increases and broadening
bons. Generally, Raman spectra of disordered graphite show two decreases for depositions at 1.0 Hz repetition rate. This increase in
quite sharp modes; the G peak around 1500–1630 cm−1 and the D bands intensity confirms the reduction in the disordering level of
peak around 1330–1350 cm−1 [32,33]. The G peak is assigned to the the coatings which may be due to the increase of average substrate
E2g symmetric vibration mode of graphite layers of microdomain surface temperature and stress relaxation for higher repetition rate
in the coatings [32,33]. of 1.0 Hz. This reduction in disordering level may be attributed to
Fig. 2 shows Raman spectra of the DLC coatings at different the minimization of total free energy of the coatings and conse-
angular positions (0◦ , 10◦ and 20◦ ) for repetition rates of (a) quently results in the crystal growth. Thus, the band growth and
0.5 Hz and (b) 1.0 Hz. For both the deposition rates, Raman spectra broadening of the D and G bands strongly depend on the repetition
 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195 191

Fig. 4. Typical X-ray diffractograms of the DLC coated SS samples at different angular
positions (10◦ and 20◦ ) for 1.0 Hz repetition rate, showing (1 1 1) and (2 0 0) plane
orientations of the ␥ phase, and (1 1 0) plane of restructured ␣-Fe phase in AISI 304
SS substrate.

The DLC coatings have significant but varied amount of sp2 and
sp3 bonding, possible clustering of similarly bonded carbon atoms
to provide some short range order, and very small or large amount
of hydrogen. The variation of ID /IG at different angular positions
for two different repetition rates tracks the sp2 /sp3 content varia-
tion (or the DLC character) of the coatings. Thermal desorption of
bonded hydrogen takes place during rapid heating of the coating
surface. Eventually, hydrogenated amorphous carbon may trans-
form to non-hydrogenated one and vice versa depending upon
substrate position. For example for a particular repetition rate,
Fig. 3. Variation of ID /IG ratio and G band position in the DLC coating as a function DLC coatings evolve from a-C to a-C:H owing to less efficient ther-
of angular position of the sample for repetition rates of (a) 0.5 Hz and (b) 1.0 Hz. mal desorption of hydrogen at larger angular position exposed to
reduced ions flux of DPF. Thermal desorption of DLC coatings in
rate and hence the time-averaged substrate surface temperature terms of their thermal stability has also been studied by Tallant
rise owing to the successive focus shots. et al. [41] who showed that DLC coatings are structurally stable up
The D band to G band intensity ratio and G band peak positions to about 260 ◦ C even in high humidity or boiling water.
have been commonly used for the characterization of amorphous Thus, 1.0 Hz repetition rate and 10◦ angular position are suitable
DLC content and the induced stresses in the coatings respectively. parameters for the quality DLC coatings. Lower angular position
Such compressive internal stresses in diamond and DLC coatings of 10◦ as compared to 20◦ favors hydrogen evolution that has a
were related to the microstructure of the coatings [38]. Fig. 3 shows well-established causative relationship to the observed sp3 to sp2
the plots of the band intensity ratio (ID /IG ) and the G band position conversion owing to increased ion fluence having same effect as
(cm−1 ) as a function of angular position for two different repetition that of heating. Notably, 0◦ angular position is not favorable owing
rates; 0.5 and 1.0 Hz of focus shots. The sp2 -bonded carbon trapped to deprived surface uniformity, although having significant sp2 con-
in the sp3 -bonded diamond crystallites or in the grain boundaries tent for both repetition rates, and micro-hardness reported in later
causes more lattice strains in the diamond coating. The plot in section.
Fig. 3a shows that with change in angular position from 0◦ to 20◦ for
0.5 Hz repetition rate, the band intensity ratio increases suggesting 3.2. XRD analysis
relatively decreased sp3 content in the coating. Moreover, there is
up-shift in the G band position showing the increased vibrational Fig. 4 shows the typical XRD pattern of AISI 304 samples
frequency under reduced stresses. The decrease in the number of deposited with DLC coatings at 10◦ and 20◦ angular positions with
four-fold coordinated carbon atoms (sp3 ) with the increased value respect to the anode axis, for the focus shot repetition rate of 1.0 Hz.
of intensity ratio as well as G band peak position has well been For the pristine AISI 304 sample, the diffraction peaks appear at a 2
demonstrated by many authors [39,40]. The plot in Fig. 3b shows value of 43.5◦ and 50.4◦ respectively corresponding to (1 1 1) and
that with change in angular position from 0◦ to 20◦ for 1.0 Hz repe- (2 0 0) plane orientations of the ␥ phase of AISI 304 SS. The XRD
tition rate, the band intensity ratio decreases, that shows increased spectra obtained clearly show the emergence of ␣-Fe (1 1 0) peak
sp3 content in the coating. It is also supported by down-shift of at 44.31◦ owing to stress induced restructuring/phase transforma-
the G band position owing to reduced vibrational frequency under tion in SS. Zeb et al. [42] also deposited amorphous DLC coatings
applied stresses. on Si (1 0 0) using a low energy (1.45 kJ) dense plasma focus. They
192 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195

observed the XRD peak as asymmetric broad humps at 2 ≈ 44◦ and micrograph taken at magnification of ×40,000 (Fig. 5a), the patchy
attributed it to the formation of lattice defects in the silicon after or layered profile of the DLC coatings can be clearly identified. Since
ion irradiation. the deposition is done in multiple shots, there might be multi-
DLC phase appearance is owing to the impact of short pulse layers composed of nanoparticles. The layered regions are probably
(∼100 ns) instability accelerated energetic carbon ions which can coagulated zones. The grain size of ∼40–60 nm with some size dis-
be implanted on the substrate surface and also due to the con- persion is observed on the DLC coating deposited at 10◦ angular
densation of the high temperature high density carbon plasma, position. Such granular surfaces with significant thermal coagula-
from the dissociation of filling CH4 gas in DPF chamber, on the tion effects have also been early reported in our previous work [24].
SS substrate typically lasting for few microseconds. As the depo- These coagulated regions are developed due to the high energy flux
sition is conducted using multiple focus shots fired at repetition of instability accelerated ion beams emitted from the NX2 operated
rates of 0.5 and 1.0 Hz, the very high flux energetic carbon and at high repetition rate usually at lower angular position of the sub-
hydrogen ions from subsequent shots can cause the melting and strate. This can be elaborated under the theory of charged clusters
subsequent rapid cooling of the carbon coated SS substrate surface. (TCCs) [47] and the thermal coagulation phenomenon. The DPF ions
This results in the recrystallization of SS substrate surface along and/or radicals, having multiple charged states [15], nucleate in the
with that of carbon layer deposited up to previous focus shot due gas phase to form charged nucleates, which are then deposited on
to the adsorption of energetic species (mostly carbon ions) onto the the substrate to form coating. A large amount of energy transferred
surface thus forming new phases [43]. The cooling of surface devel- to the substrate via electronic excitations develops defects and con-
ops amorphous regions and defects within the bulk [44]. The DPF sequently nanostructures of nm scale nucleates. The nucleates can
ion adsorbate-induced reconstruction yields new structures with grow either by reactions with reactive species in the gas phase or
the minimization of the surface free energy of substrate and the combining with very small uncharged clusters. These nucleates are
coating. This is also accompanied by the introduction of stresses grown by the ion-induced collision cascades and extend to a range
to the system. The stresses have one major advantage of hardness of up to a few tens of nm for ion energies of several tens of keV
improvement. The presence of tensile stresses in the DLC coatings to MeV [48]. The DLC coatings obtained at 20◦ angular position
is observed by the downshift of the carbon peak position in the XRD have almost identical morphology, whereas those at 0◦ have slight
spectrum, when compared with the standard stress free data. This damage owing to the high energy ions.
indicates a uniform stress developed normal to the corresponding The energetic impacts from highly ionized hot dense CH4 plasma
crystal plane in the film during rapid cooling after transient tem- leads to the formation of sp3 -bonded carbon in a sp3 -bonded sub-
perature rise by ion irradiation. The tensile stresses in DLC coatings strate surface matrix. The surface structure may have a hydrogen
are owing to the incorporation of energetic (up to few hundreds and sp3 hybridized carbon enriched surface. During multiple shots
of keV) carbon species interstitially (up to a few hundreds of nm irradiation, the coatings developed with previous shots are hydro-
depending on ion energy range) in addition to their presence as genated by exposing them to the ionic and/or atomic hydrogen
bonded C in sp2 and sp3 . Similar effect of N2 ion implantation on beams, leading to the transformation of sp2 hybridized carbon
AISI 304 has revealed that the initial compression residual stresses groups to sp3 hybridized groups at the coating surface. This depends
were changed to tensile stresses after ion implantation. The resid- on the H/C ratio in CH4 plasma at any angular position. Since carbon
ual stress gradient, induced in the implanted surfaces, was found to content is high at lower angular position (0◦ and 10◦ ), sp2 -enriched
become more significant with the increase of ion beam fluence. The dominates at these positions. The implanted ions displace pre-
DPF ions induced stress evolution and transformation from com- dominantly bonded hydrogen owing to lower threshold energy for
pressive to tensile or vice versa have extensively been reported hydrogen, compared to that of carbon [49]. The displaced hydro-
already [21,45,46]. gen atoms can recombine with a lattice defect or form H2 molecules
From Fig. 4, it is clear that the DLC coating at 20◦ angular posi- by atomic recombination. The H2 molecules are either trapped in
tion has less stresses as compared to that achieved at 10◦ angular internal voids or diffuse to the surface and desorb. This leads to the
position due to low energy flux at 20◦ position. Our previous results phase transition from polymer-like structure to the diamond-like
on DPF based coatings strongly support this evidence [20,21]. structure with low hydrogen content and an increase in the coating
The average crystallite size is calculated from the ␣-Fe (1 1 0) density. Thus, the ion-induced compression of polymer-like sp3 -
peak width using the Scherrer formula bonded structure to a denser sp2 -enriched phase is resulted from
strong thermal spikes during DPF ion irradiation.
K The EDS map of the coating exhibit the distribution of elements
crystallite size = ,
ˇ cos  present in the coating using the imaging energy filters. By selecting
the area of the SEM image for mapping and spectrum acquisition
where K = 0.99 is the numerical constant,  = 1.540598 Å is the
(Fig. 5c), the elemental distribution of the elements surface coating
wavelength of X-ray source, ˇ is the broadening (in radians) of the
can be obtained. In mapping, an image of the sample will be made
diffraction peak and  is the Bragg’s angle. The average crystallite
that is simply the intensity of a particular emission mapped in an
size of ␣-Fe in restructured SS 304 varies from ∼40 to 50 nm.
XY raster. The intensity of the particular X-ray lines in the maps
is qualitative measure of elemental distribution. Fig. 5d shows the
3.3. SEM/EDS SEM dark image used to collect the EDS map on the same scale.
Fig. 5b shows the CK␣ map presenting the elemental distribution
Scanning electron microscopy (SEM) and energy dispersive X- of carbon on the DLC coating surface. The intensity of the CK␣ in
ray spectroscopy (EDS) were carried out for the morphological and the maps is a qualitative measure of the elemental concentration.
elemental analysis of the coatings. Fig. 5 shows the SEM micro- A homogeneous spatial distribution of the CK␣ emission indicates
graph, EDS map, SEM dark image taken at working distance of the spatially uniform carbon over the DLC coated SS sample surface
15 mm showing area selection for EDS map and spectrum acqui- macroscopically.
sition, dark image of EDS map and EDS spectrum recorded for a Fig. 5e shows the EDS spectrum of the above mentioned
typical sample with DLC coating achieved on 10◦ angular posi- coating. The incorporation of C content is evident in the spectrum,
tion for 1.0 Hz repetition rate. The coating appears golden in color along with the presence of SS composition. The carbon content
when viewed visually. Such type of color appearance reports the in pristine AISI 304 steel is 0.08 wt.%, which is much less than the
amorphous, polymeric nature of the DLC coatings. From the SEM values obtained for DLC coated SS. The EDS spectra demonstrate
 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195 193

Fig. 5. (a) Typical SEM micrograph of the DLC coatings with coagulated regions due to ions assisted thermal effects, (b) CK␣ EDS map, (c) SEM dark image to select area for
EDS map and spectrum acquisition, (d) dark image of the EDS map and (e) EDS spectrum of the DLC coatings deposited at the angular position of 10◦ for 1.0 Hz repetition
rate.

the increase in carbon concentration depending on the angular Thus, appearance of carbon content in sp2 -enriched phase shows
position. For the DLC coatings obtained for 0.5 Hz repetition that the 10◦ angular position and 1.0 Hz repetition rate provide the
rate, the concentration of carbon varies from 10.1 at.% to 5.2 at.% optimum deposition conditions in the present experiment.
(3.31 ± 1.22 wt.% to 2.12 ± 0.88 wt.%) when the sample position is
shifted from 0◦ to 20◦ with respect to anode axis. Whereas, for the 3.4. Micro hardness measurements
DLC coatings obtained for 1.0 Hz repetition rate, the carbon con-
centration is reduced from 14.21 at.% to 7.82 at.% (4.31 ± 1.22 wt.% Fig. 6 shows the surface hardness (GPa) of DLC coatings as a
to 2.81 ± 0.79 wt.%) when the sample position is shifted from 0◦ to function of the indentation depth (␮m) with different test loads on
20◦ . The carbon concentration data has been provided in Table 2. the sample surfaces treated at various angular positions for 1.0 Hz
It has been found that the C content is significantly reduced at repetition rate. The maximum surface hardness is found for DLC
higher angular position. The reduction in carbon content at the coatings at 0◦ angular position. The typical micro-hardness of the
20◦ angular position is due to the reduced ion fluence impinging at DLC coatings is around 3 GPa. However, in the near surface region,
this position of the substrate. Moreover, the C content is found to it approaches to 6 GPa. It is noted that the relatively lower values of
reduce with the repetition rate reduction also, showing deprived microhardness are obtained at higher angular position in spite of
quality of the DLC coatings due to lesser temperature assistance. higher sp3 content in DLC coatings. This fact may be attributed to

Table 2
EDS data showing the carbon concentrations (at.% and wt.%) in DLC coated SS surfaces at different sample positions for two different repetition rates.

Sample identification Repetition rate 0.5 Hz Repetition rate 1.0 Hz

0◦ position 10◦ position 20◦ position 0◦ position 10◦ position 20◦ position

C content (at.%) 10.1 8.62 5.2 14.21 11.86 7.82

C content (wt.%) 3.31 ± 1.22 3.04 ± 0.92 2.12 ± 0.88 4.31 ± 1.22 3.78 ± 1.02 2.81 ± 0.79
194 M. Hassan et al. / Applied Surface Science 303 (2014) 187–195

owing to stress induced disorder in the SS lattice, having crystallite

size estimated to be ∼40–50 nm. The repetitive ion bombardment
has played an important role in surface transient temperature rise
and eventual less strained DLC coating in comparison with low
repetition rate plasma focus ions bombardment. The surface micro-
hardness of the coatings achieved at 10◦ angular position has been
increased three times for repetition rate of 1.0 Hz.

Acknowledgements

One of the authors (Dr. M. Hassan) is grateful to the NESCOM

for providing financial support to carry out experimentation and
materials analysis at Nanyang Technological University (NTU),
Singapore. One of them, S. Mahmood would like to thank NIE, NTU
for providing the research scholarship.

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