Surface & Coatings Technology 309 (2017) 164–171

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Surface & Coatings Technology

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

Characterization of Al-Mg-B-C films based on experimental and

first-principles investigations
V.I. Ivashchenko a,⁎, S.N. Dub b, P.L. Scrynskyy a, A.O. Kozak a, Leonid Gorb c,d, Frances Hill e, Jerzy Leszczynski c
a
Frantsevych Institute for Problems of Material Science, NAS of Ukraine, 3, Krzhyzhanovsky Str., 03142 Kyiv, Ukraine
b
Bakul Institute for Superhard Materials, NAS of Ukraine, 2, Avtozavodska Str., 04074 Kyiv, Ukraine
c
Department of Chemistry and Biochemistry, Interdisciplinary Center for Nanotoxicity, Jackson State University, Jackson, MS 39217, USA
d
Badger Technical Services, LLC, Vicksburg, MS 39180, USA
e
U.S. Army ERDC, Vicksburg, MS 39180, USA

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

Article history: Al-Mg-B and Al-Mg-B-C films were deposited by DC magnetron sputtering from the AlMgB14 and B4C targets on
Received 15 March 2016 silicon substrates at different discharge power densities at both the targets. The deposited films were character-
Revised 23 June 2016 ized by atomic force microscopy, X-ray diffraction, transmission electron microscopy, Fourier transform infrared
Accepted in revised form 14 July 2016
spectroscopy, X-ray photoelectron spectroscopy, nanoindentation, scratch and pin-on-disk testing. All the depos-
Available online 15 July 2016
ited films were found to be X-ray amorphous. The film roughness, nanohardness and elastic modulus increase
Keywords:
with the discharge power densities at both targets. An introduction of carbon is accompanied by the formation
DC magnetron sputtering of the strong C-B4 units that strengthen Al-Mg-B-C films. The films exhibit a coefficient of friction in the range
AlMgB14 of 0.09–0.20. First-principles calculations show that the amorphous AlMgB14-based materials consist of the frag-
B4C ments of boron icosahedra, for which reason they possess the hardness that is lower than the hardness of the
Chemical bonding crystalline counterparts. Based on experimental and theoretical results, it is assumed that the observed strength
Nanoindentation enhancement can be assigned to an improvement of the B-B icosahedron-like network and film densification.
First-principles calculations © 2016 Elsevier B.V. All rights reserved.

1. Introduction wear-resistant, protective and self-lubricating coatings for cutting

Hard materials based on AlMgB14 (so-called BAM materials) have
the orthorhombic 64-atom unit cell (space group Imma, No. 74) that
consists of four icosahedra (B12 units), eight inter-icosahedron boron
atoms and metal atoms that are located in interstices between the ico-
sahedra and are bonded to the icosahedra via the inter-icosahedron
boron atoms [1]. The occupancy of the Al and Mg sites are ~ 75% and
78%, respectively, which corresponds to a composition for the material
of Al0·75Mg0.78B14 [1]. The bulk BAM materials posses high hardness of
25–35 GPa, low friction coefficient and chemical inertness [2,3]. Other
BAM structures, so-called ternary compounds, such as MgC2B12 and
LiC2B12 crystallize also with the orthorhombic lattice. This crystal struc-
ture can be characterized by nearly hexagonal layers formed by cova-
lent-connected B12 units. C2 and Mg (Li) atoms occupy the trigonal
prismatic voids between the layers. These compounds exhibit hardness
above 33 GPa [4]. The BAM materials are very promising candidates as
⁎ Corresponding author.
E-mail address: ivash@materials.kiev.ua (V.I. Ivashchenko).
tools, microdevices and microelectromechanical systems [5–7].
The brief review of the deposition procedures and properties of BAM
bulk and film structures was given in Ref. [5]. Here we note that the
films based on BAM structures were studied not so comprehensive
compared to the bulk materials. In particular, it was established that
the nanohardness (H) and elastic modulus (E) of the films were very
sensitive to the deposition conditions and method used, changing in
the range of 7–51 GPa and 80–300 GPa, respectively [6–11]. Mostly
the films were prepared by pulsed laser deposition [6–8] and magne-
tron sputtering [9–12]. The targets for sputtering were composed of
AlMgB14, AlMgB14 + 20%TiB2, Al, Mg and B. The films were found to
be amorphous [6–11] and the annealing at 1200 °C did not lead to crys-
tallization [6]. The authors [12] succeeded in the preparation of the
nanocryatalline films at a low target power density (~1.1 W/cm2). To
our knowledge, the systematic investigations of the influence of dis-
charge power density and an introduction of carbon on the properties
of the BAM-based films were not carried out.
In this work we investigate the effect of both discharge power den-
sity and an introduction of carbon on the structural and mechanical
properties of the Al-Mg-B-C films prepared by DC magnetron sputtering

http://dx.doi.org/10.1016/j.surfcoat.2016.07.044
0257-8972/© 2016 Elsevier B.V. All rights reserved.
 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171
from the AlMgB14 and B4C targets. It was expected that carbon incorpo-
ration would promote strength enhancement of BAM-based films [4].
To interpret the properties of the deposited films, first-principles inves-
tigations of crystalline and amorphous BAM structures were carried out.
2. Experimental and theoretical procedures
2.1. Film preparation
The films were deposited by balanced DC magnetron sputtering
from the AlMgB14 and B4C targets (the disks with the diameter and
thick of 72 mm and 4 mm, respectively, purity 99.9%) simultaneously
at different discharge power densities at the AlMgB14 (PBAM) and B4C
(PB4C) targets. The apparatus was designed to deposit coatings by co-
sputtering two targets. The angle between the axes of the magnetron
devices directed to the center of a substrate holder was 86°. A rotating
substrate holder was located 8 cm away from the targets. Three sets of
films (A, B and C) were prepared. The discharge power densities were:
PBAM = 1.2, 1.7, 2.3, 3.1, 3.8 and 4.6 W/cm2, PB4C = 0 (set A); PBAM =
1.1, 2.5, 3.3 and 4.1 W/cm2, PB4C = 1.0 W/cm2 (set B); PB4C = 0, 1.0,
2.2 and 3.4 W/cm2, PBAM = 3.8 W/cm2 (set C). The substrate tempera-
ture and substrate bias were 500 °C and − 50 V, respectively. The
argon flow rate and working pressure were 51 sccm and 0.17 Pa, respec-
tively. The vacuum chamber was pumped down to a background pres-
sure of 10− 3 Pa by a turbomolecular pump. The substrates were
polished Si (100) wafers. Before the deposition, the silicon wafers
were cleaned in the bath with a 5% HF solution to remove the native
oxide. Afterwards, the substrates were rinsed in de-ionized water and
dried in nitrogen. Finally, they were sputter-etched in argon plasma in
the chamber prior to the deposition. Below, we will use the abbreviation
for our films. For an example, A-1.2 means that the film was deposited at
PBAM = 1.2 W/cm2, PB4C = 0 (set A). We prepared two kinds of the films
– Al-Mg-B (set A) and Al-Mg-B-C (sets B and C). In Table 1, we present
the thicknesses of the films (D), as well as their friction coefficients (μ)
and critical loads of peeling (Nc) that will be discussed below. As to film
thickness, we note that this value increases with discharge power den-
sity, however, the sputtering of a growing film at the highest PBAM (set
A) and PB4C (set C) slows down film growth (cf. Table 1).
2.2. Film characterization
The structure of the films was analyzed by X-ray diffraction (XRD) (a
diffractometer “DRON-3 M”) using Cu Kα radiation. The microstructure
of the film deposited at PBAM = 4.6 W/cm2 and PB4C = 0 (A-4.6) was ex-
amined with a JEM100CX transmission electron microscope (TEM) op-
erated at 100 kV. The film surface was studied by means of an atomic-
force microscope (AFM) “NanoScope IIIa Dimension 3000TM”, and the
chemical bonding by Fourier transform infrared spectroscopy (FTIR)
using a “FSM 1202” LLC “Infraspek” spectrometer. The chemical states
were studied by an EC 2401 X-ray photoelectron spectroscopy (XPS)
using Mg Kα X-ray radiation (E = 1253.6 eV). The Au 4f7/2 and Cu
2p3/2 peaks with binding energy of 84.0 ± 0.05 eV and 932.66 ±
0.05 eV, respectively, were used as a reference. A pass energy was
Table 1
Discharge power density (PBAM, PB4C), film thickness (D), friction coefficient (μ) and critical load (Nc) for three sets of films.
A B
(PB4C = 0) (PB4C = 1.0 W/cm2)
PBAM D μ Nc PBAM
(W/cm2) (μm) (N) (W/cm2)
1.2 0.7 0.085 N0.3 1.1
1.7 0.7 0.130 N0.3 2.5
2.3 0.7 0.131 N0.3 3.3
3.1 1.3 0.134 N0.3 4.1
3.8 1.6 0.147 N0.3
4.6 1.2 0.150 N0.3
165
50 eV. The films were etched for 5 min with 1.8 keV Ar+ ions to remove
surface contaminations. The nanoindentation of the films was carried
out under a continuous stiffness measurement (CSM) mode using a
Nano Indenter-G200 system (Agilent Technologies). This mode allows
one to perform a continuous measurement of the contact stiffness via
a superimposed alternating current signal during loading, which, in
turn, provides a continuous measurement of the elastic modulus (E)
and hardness (H) as functions of indenter displacement (L) during a
single loading segment [13]. All the nanoindentations were produced
with a Berkovich diamond tip of a nominal radius equal to ~ 340 nm.
Area function was calibrated from indentation on a standard fused silica
specimen. Eight indentations were made on each sample. The load and
displacement were continuously recorded up to a maximum displace-
ment of 200 nm at a constant indentation strain rate of 0.05 s−1. The
CSM frequency was 45 Hz, and the amplitude of oscillation was 2 nm.
The nanohardness and elastic modulus were determined as the maxi-
mum values in the H(L) and E(L) dependences, respectively, in the
range of 0 b L b 0.1D (where D is a thickness of the films). The thickness
of the films was estimated by a “Micron - alpha” optical profilometer.
The scratch tests were performed with a “Micron-gamma” scratch tes-
ter using a Vickers diamond pyramidal tip with a linear scan rate of
9 μm/s and a ramping load from 0 to 0.3 N. Also, the coefficient of fric-
tion of the samples C was evaluated using pin-on-disk unidirectional
sliding at room temperature. Fixed bearing ball of Si3N4 with a diameter
of 3 mm was used as the slider. The disk rotation speed was 60 rpm. The
pin-on-disk tests were conducted in an ambient air environment with
an applied normal load of 0.2 N and sliding speed of 0.03 m/s for
18.84 m sliding distance. The typical value of the fiction coefficient for
the C films was around 0.2.
2.3. Computational aspects
It was found that AlMgB14-based materials (space group Imma, No.
74) could be formed with deficiency of the metal atoms with the formu-
la unit Al0·75Mg0.78B14 [1]. Given this fact, we investigated the mechan-
ical properties of crystalline (c) and amorphous (a) AlMgB14 and
Al0·75Mg0.75B14 structures. For this purpose, we singled out the initial
orthorhombic 64-atom supercell with the composition of Mg8B56
(space group Imma, No. 74) [14]. The initial structures Al4Mg4B56 and
Al3Mg3B56 were constructed by means of the substitution of the Mg
atoms by Al atoms. For the investigation of c-Mg4B48C8, in the lattice
of c-Mg8B56, the four Mg atoms were removed, and the eight inter-
icosahedral B atoms were substituted by the eight C atoms.
The first-principles calculations were performed with the quantum
ESPRESSO code [15] using periodic boundary conditions and the gener-
alized gradient approximation (GGA) of Perdew, Burke and Ernzerhof
(PBE) [16] for the exchange-correlation energy and potential. Vander-
bilt ultra-soft pseudo-potentials were used to describe the electron-
ion interaction [17]. The cut-off energy of 36 Ry (489.6 eV) was used.
The structural optimization was carried out by simultaneously relaxing
the supercell basis vectors and the atomic positions inside the supercell
using the Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm [18].
The relaxation of the atomic coordinates and of the supercell was
C
(PBAM = 3.8 W/cm2)
D μ Nc PB4C D μ Nc
(μm) (N) (W/cm2) (μm) (N)
0.7 0.170 0.188 0.0 1.6 0.147 N0.3
0.7 0.160 0.263 1.0 1.8 0.134 N0.3
0.8 0.108 0.275 2.2 1.9 0.120 0.208
1.8 0.134 N0.3 3.4 1.2 0.130 0.107
166 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171
considered to be complete when atomic forces were b 1.0 mRy/Bohr
(25.7 meV/Å), stresses were smaller than 0.05 GPa, and the total energy
during the structural optimization iterative process was changing by
b0.1 mRy (1.36 meV). The geometry optimization was carried out
using the (6 4 3) Monkhorst-Pack mesh [19].
The quantum molecular dynamics (QMD) calculations of the initial
relaxed structures were carried out with fixed unit cell parameters
and volume (NVT ensemble, constant number of particles-volume-tem-
perature). First, the structures were let to evolve at 4500 K for 4 ps, and
then the melts were cooled down to 300 K during 20 ps. In the QMD cal-
culations, the time step was 20 a.u. (about 10−15 s). The system temper-
ature was kept constant by rescaling the velocity. In the large-scale
QMD simulation, the chosen reduced k-points mesh (222) were used
in order to save computing time without compromising accuracy [20].
The elastic moduli of both crystalline and amorphous BAM struc-
tures were calculated using the first-principles “ElaStic” code [21]. The
intrinsic hardness was estimated using calculated shear moduli in the
framework of the approach [22]. The shear stress of the structures was
calculated as follows: first, an incremental shear distortion was im-
posed, then the dihedral angle between the supercell vectors that corre-
sponds to the given shear was fixed, and simultaneously the basis
supercell vectors and the atomic coordinates were relaxed. For shear
strains the structural parameters at a previous step were used to calcu-
late the Hellmann-Feynman stress for the next step.
3. Results and discussons
3.1. Experimental investigations
The AFM images of the films deposited at different discharge power
densities PBAM and PB4C are shown in Fig. 1. The root mean square (RMS)
roughness of the films was determined at the area of 2 μm × 2 μm. This
value increases from 4.6 nm to 5.6 nm with increasing PBAM from
1.2 W/cm2 to 3.8 W/cm2 (PB4C = 0.0) (cf. Fig. 1 (a) and (b)), as well
as from 2.3 nm to 3.0 nm as PBAM increases from 1.1 W/cm2 to
4.1 W/cm2 (PB4C = 1.0 W/cm2) (cf. Fig. 1 (d) and (e)). An increase of
PB4C from 0 to 3.4 W/cm2 (PBAM = 3.8 W/cm2) leads to an increase in
RMS from 5.6 nm to 6.5 nm (cf. Fig. 1 (b) and (c)). These data show
that the roughness of the films surfaces increases with increasing dis-
charge power densities at both targets.
We analyzed the XRD patterns of the deposited films (not shown
here) and did not find the reflexes related to any crystallites, for
which reason we assumed that the films were X-ray amorphous. Fig. 2
shows the plan-view TEM image of the A-4.6 film. The amorphous
structure of the film is indicated by the halo ring in the selected area
Fig. 1. AFM images of the surfaces of the films: A-1.2 (PBAM = 1.2 W/cm2, PB4C = 0), RMS = 4.6 nm (a); A-3.8 (PBAM = 3.8 W/cm2, PB4C = 0), RMS = 5.6 nm (b); C-3.4 (PBAM = 3.8 W/cm2,
PB4C = 3.4 W/cm2), RMS = 6.5 nm (c); B1̄.1 (PBAM = 1.1 W/cm2, PB4C = 1.0 W/cm2), RMS = 2.3 nm (d); B-4.1 (PBAM = 4.1 W/cm2, PB4C = 1.0 W/cm2), RMS = 3.0 (e).
Fig. 2. Bright-field TEM image of the film A-4.6 (PBAM = 4.6 W/cm2, PB4C = 0). The insert is
the selected area diffraction pattern from the film.
diffraction pattern. However, the film contains very small bright inclu-
sions that can be interpreted as boron-based crystallites, or boron icosa-
hedral units [10].
The FTIR spectra of the films deposited at different discharge power
densities are shown in Fig. 3. The roman numerals indicate the location
of the absorption bands related to the B-O-B bending and B-O stretching
vibrations in the tetragonal BO4 and trigonal BO3 units [23,24]. Also, we
note that B-C vibrations (~1100 cm−1) [25], inter-icosahedron B-B vi-
brations (1060–1180 cm−1) [9,10] and C-C vibrations (~ 1250 cm−1)
[26] can contribute to the absorption bands in the range of 1060–
1250 cm−1. It is seen that an increase of the discharge power density
PBAM leads to reducing the intensity of B\\O vibrations (band III) and
to strengthening inter-icosahedron B-B vibrations (bands I and II) (cf.
Fig. 3 (a) and (b)). For the films of the set C, we did not reveal a marked
trend in the FTIR spectra (cf. Fig. 3 (c)), which is due to the presence of a
large number of different bonds, such as B\\O, B\\B, B\\C and C\\C
ones, that form the absorption bands I, II and III.
To gain more insight into the chemical bonding we measured the
XPS core-level spectra for the deposited films belonging to different
sets. In Figs. 4 and 5, the results of the measurements are presented.
We used the literature data [6,10,27–35] for an identification of the
peaks in the measured spectra. The XPS Al 2p spectrum of the A-1.2
coating shows the one main peak that can be assigned to Al\\O bonding
[27]. The shift of this peak towards high binding energies (BE) with an
increase of the discharge power density at both targets is considered
as the strengthening of the Al\\B bonds [28]. An analysis of the XPS
Mg 2 s spectra shows that, for the A-1.2 film, the Mg\\O bonds are pre-
dominant [6,29], whereas the main bonds in the A-3.8 and C-3.4 films
 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171
Fig. 3. FTIR spectra of the films of the sets A (a), B (b) and C (c). Arabic numerals are the discharge power densities in W/cm2 (PBAM, PB4C). Absorption bands I, II and III are localized around
1060–1100, 1150–1180 and 1250 cm−1, respectively.
are Mg\\B ones [29]. There are a peak and a shoulder in the B 1s spectra.
The shoulder at about 192 eV originates from B\\O bonds in B2O3 [6,30],
whereas the peaks around 188.6–189.1 eV are characteristic for Al-
borides [10]. The peaks assigned to the B\\B bonds at binding ener-
gies in the range of 187.4–188.0 eV were revealed in AlMgB14 [30]
and Al0·84Y0.75B14 [31] films. A weak feature in the spectrum of the
C-3.4 film around 190.7 eV can be assigned to B\\C bonds [32]. It is
seen that an increase in both PBAM and PB4C leads to strengthening
the borides and B\\B bonds. The peak in the O 1s spectrum of the A-
1.2 film corresponds to boron oxide [33]. For the high-powered films,
the Mg\\O bonds are predominant [34]. The XPS C 1s spectrum of the
C-3.4 film can be fitted by two Gaussians that are assigned to the C\\C
bonds in amorphous carbon and the C\\B bonds in amorphous B4C
Fig. 4. XPS core level spectra from the A1̄.2 (PBAM = 1.2 W/cm2, PB4C = 0) (dotted line),
A-3.8 (PBAM = 3.8 W/cm2, PB4C = 0) (solid line) and C-3.4 (PBAM = 3.8 W/cm2, PB4C =
3.4 W/cm2) (dashed line) films. The vertical lines denote the binding energies at:
75.8 eV Al\ \O bonding in non-stoichiometric Al2O3 [27], 75.01 eV, Al\ \B bonding [10],
74.1 eV in MgAl2O4 [28] for the Al 2p spectra; 90.85 eV Mg\ \O bonding [6], 90.1 eV
Mg\ \B bonding in MgB2 [29] for the Mg 2 s spectra; 191.88 eV B\ \O bonding [6],
190.7 eV B\ \C bonding [32], 188.6 eV Borides [10] and 187.62 eV B\ \B bonding [10] for
the B 1s spectra; 533.3 eV B\ \O bonding [33], 532.9 eV Mg\ \O bonding [34] and
531.8 eV Al\ \O bonding [35] for the O 1 s spectra.
167
[32] (cf. Fig. 5). It follows that, in Al-Mg-B-C films, carbon mainly
forms C\\C and C\\B bonds.
The characteristic feature of the Al 2p, Mg 2s and B 1s spectra is the
shift of the mean peaks towards high binding energies with increasing
discharge power density. These findings show that there are Al-B and
pure B units, as well the fragments of the Al2O3, MgO, B2O3, MgAl2O4
and possibly other oxide configurations in the amorphous films, and
the increase in discharge power density promotes the formation of
new metal-boron, boron-boron, boron-carbon and magnesium–oxygen
bonds. Using the measured XPS spectra, we estimated the elemental
composition of Al-Mg-B and Al-Mg-B-C films. The estimated concentra-
tions of Al, Mg, B, C and O in the films deposited at various PBAM and PB4C
are summarized in Table 2. Oxygen is abundant in the deposited films
due to absorption of water and oxygen species during sample exposure
to air [5,6]. The oxygen content decreases with increasing in discharge
power densities (cf. Table 2).
One can see from Figs. 3–5 that the FTIR and XPS investigations pre-
dict the presence of the B\\O, Al\\O, Mg\\O, B\\B and Al\\B bonds in
amorphous Al-Mg-B films. The B\\B, Al\\B and Mg\\O bonds strength-
en, and the B\\O bonds weaken, when PBAM increases. For Al-Mg-B-C
films, C\\C and C\\B bonds were additionally detected.
The nanohardness and elastic modulus of the deposited films are
presented in Fig. 6 as functions of indentation depth (L). The depen-
dences of the values of H and E on discharge power densities are
shown in Fig. 7. The nanohardness and elastic modulus of the amor-
phous low-powered film are compared to those of the silicon substrate
Fig. 5. Deconvolution of the XPS C1 s spectrum of the C-3.4 (PBAM = 3.8 W/cm2, PB4C =
3.4 W/cm2) film by Gaussians. Two Gaussian peaks at 284.3 eV and 282.8 are assigned
to C\\C bonding in a-C (284.5 eV) and to B\ \C bonding in amorphous B4C (283.0 eV)
[32], respectively.
168 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171

Table 2
Elemental composition of the films estimated from XPS measurements.

Coating Al Mg B C O
(at.%) (at.%) (at.%) (at.%) (at.%)

A-1.2 6.1 1.9 60.0 – 32.0

A-3.8 5.4 3.0 66.4 – 25.2
B-4.1 4.3 5.0 60.7 5.1 24.9
C-3.4 4.4 2.3 58.2 8.1 27.0

(12.5 GPa and 140 GPa, respectively). Figs. 6 and 7 show that the
nanohardness and elastic modulus increase with PBAM. An additional
sputtering from the B4C target during film deposition promotes the
strengthening of the deposited films. One can see that there is an opti-
mum discharge power density (PB4C = 2.2 W/cm2) at which film hard-
ness is maximum (cf. Fig. 7, set C). It follows that the deposited
amorphous high-powered Al-Mg-B-C films exhibit the hardness
(about 30 GPa) that is comparable to the hardness of the bulk BAM
materials (25–35 GPa) [2,3]. The observed hardness enhancement is as-
sumed to be due to strengthening the B\\B, Al\\B and B\\C bonds. The
hardness of the low-powered films is lower compared to the hardness
of the bulk BAM materials, which can be assigned to the amorphous na-
ture of the these films in which the strong B\\B bonds are almost absent
and the weaker B\\O bonds are predominant. The more comprehensive
discussion of the possible reasons of the observed strength enhance-
ment will be done below.
The results of scratch tests are summarized in Table 1. Fig. 8 illus-
trates the dependencies of friction forces on normal load for the films
Fig. 7. Nanohardness (H) and elastic modulus (E) for the films of sets A (PBAM = 1.2, 1.7,
of the set C. From Table 1 and Fig. 8 one can see that the critical load 2.3, 3.1, 3.8, 4.6 W/cm2, PB4C = 0) , B (PBAM = 1.1, 2.5, 3.3, 4.1 W/cm2, PB4C = 1.0 W/cm2),
(a load at which a film starts to delaminate) increases with PBAM and de- and C (PBAM = 3.8 W/cm2, PB4C = 0, 1.0, 2.2, 3.4 W/cm2) as functions of discharge power
creases with increasing PB4C. It follows that an increase in PBAM pro- densities (PBAM, PB4C).
motes the enhancement of the film adhesion to silicon substrates,
whereas an increase of the discharge power density at the B4C target matrix. Also, the amorphous carbon inclusive in the Al-Mg-B-C films
has an opposite effect on film adhesion. Most likely, the latter is caused promotes a reduction of their friction coefficient, when PB4C increases.
by an incorporation of the carbon atoms in the amorphous Al-Mg-B For the Al-Mg-B films (set A), friction coefficient increases with the
discharge power density PBAM (cf. Table 2). An analysis of the results
presented in Fig. 1 and Table 1 shows that the correlation between sur-
face roughness and friction coefficient is not observed. The compara-
tively low friction coefficient evaluated from the scratch tests (0.09–
0.17) and pin-on-disk tests (~ 0.2) can be attributed to the formation

Fig. 6. Nanohardness (H) and elastic modulus (E) as functions of indentation depth (L) for
the films deposited at different discharge power densities PBAM = 1.2, 1.7, 2.3, 3.1, 3.8 and Fig. 8. Friction force as a function of load for the films of the set C (PBAM = 3.8 W/cm2,
4.6 W/cm2, PB4C = 0 (set A). The curves are arranged from bottom to top with increasing PB4C = 0, 1.0, 2.2, 3.4 W/cm2). Arabic numerals are the discharge power densities PB4C
PBAM. (in W/cm2). Arrows indicate the critical loads (Nc).
 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171 169

Fig. 9. Supercells of c-Mg4B48C8 (a), c-Al3Mg3B56 (b) and a-Al3Mg3B56 (c).

of a very lubricious surface layer of boric acid that acts as self-lubricant
for BAM-based films [30].
3.2. Theoretical investigations
We have carried out both the geometry optimization and QMD cal-
culations of the crystalline and amorphous BAM structures to explain
the experimental results presented above. It was found that the forma-
tion energies for c-Al3Mg3B56 (−0.103 eV/atom) was lower than for
c-Al4Mg4B56 (− 0.092 eV/atom), which means that the BAM com-
pounds will be formed with deficiency of the metal atoms in agree-
ment with the experimental [1] and theoretical [36] investigations.
The highest negative formation energy was gained for c-Mg4B48C8
(− 0.139 eV/atom). The amorphous Al3Mg3B56 structure is metasta-
ble, since its formation energy is positive (0.242 eV/atom).
Fig. 9 shows the supercells of c-Mg4B48C8, c-Al3Mg3B56 (after geom-
etry optimization) and a-Al3Mg3B56 (after QMD simulation with subse-
quent geometry optimization). An analysis of the atomic configuration
of the amorphous sample (cf. Fig. 9c) points out that it consists of icosa-
hedron fragments connected by the amorphous B-B network.
It is well known that the boron-based films can be prepared with dif-
ferent film densities (ρ) depending on deposition parameters and the
properties of these films are very sensitive to ρ [37]. We generated
three amorphous samples of Al3Mg3B56 with different densities: ρ b ρc
(a-e- Al3Mg3B56), ρ = ρc (a-Al3Mg3B56) and ρ N ρc (a-c-Al3Mg3B56),
where ρc is the density of c-Al3Mg3B56. This enables us to analyze the
mechanical properties of the amorphous sample depending on sample
density. We calculated the elastic moduli and estimated the intrinsic
hardness of all generated crystalline and amorphous structures at equi-
librium. The calculated Hill bulk (B), shear (G), Young's (E) modulus,
Poisson's ratio (ν) and intrinsic hardness (HI) of the crystalline and
amorphous BAM materials are presented in Table 3, and the depen-
dence of HI on sample density is shown in Fig. 10. One can see that the
calculated moduli and intrinsic hardness agree well with those gained
in other experimental and theoretical studies.
In order to investigate the behavior of the samples under finite
strains we calculated the shear stress-strain curves for the crystalline
BAM materials. The calculated shear stress-strain relations for the stron-
gest (010)[100] and weakest (001)[100] sliding systems are shown in
Fig. 11 (a and b, respectively). Such a choice of the sliding systems
allows for the layered framework structure of the crystalline BAM mate-
rials: the metal atoms in the opposite layers move in the same direction
under the (010)[100] shear, whereas they move in the opposite direc-
tions under the (001)[100] shear. The calculated ideal shear strength
for the weakest shear system (21.0–30.5 GPa) is found to be comparable
to the estimated intrinsic hardness (25.4–31.8 GPa). It follows that, for
this class of materials, the approach for the estimate of the intrinsic
hardness from the elastic moduli is quite justified. For the crystalline
BAM compounds, the highest values of the ideal strength, elastic moduli
and intrinsic hardness are reached for c-Mg4C8B48. The ideal shear
strength for this material (30–45 GPa) are comparable to that for
superhard structures such as wurtzite BN (50–60 GPa) [38] and cubic
BC5 (37–53 GPa) [39].
An analysis of the results presented in Table 3 shows that the elastic
moduli and hardness for the amorphous samples are lower as compared
to those for the crystalline counterparts. The mechanical performance of
the amorphous samples increases with sample density (cf. Table 3 and
Fig. 10).
Let us analyze the experimental results presented above. We sup-
pose that the high oxygen content in the low-powered films inhibits a
formation of the icosahedra due to the formation of B2O3-like units. As
a result, the icosahedra are not fully developed, and, according to our
calculations, such amorphous structures will possess low hardness. An
increase in the discharge power density at the sputtering targets leads
to strengthening the B\\B bonds and to weakening the B\\O ones.
This can be a sequence of the formation of the sub-nanometer icosahe-
dra embedded in the randomized B\\B matrix. The icosahedra can
aggregate to form larger units [10]. The formation of such units in the
view of very small crystallites was confirmed by the TEM investigations
(cf. Fig. 2). The hardness enhancement in such structures can occur ac-
cording to the mechanism, where the observed hardness enhancement
was explained by small crystallite sizes [40]. On the other hand, we sup-
pose also that an increase in the discharge power densities causes film
densification due to an enhancement of ion bombardment of a growing

Table 3
Calculated Hill bulk (B), shear (G), Young (E) modulus, Poisson's ratio (ν) and intrinsic hardness (HI) of AlMgB14-based compounds. For comparison, the corresponding theoretical (curly
bracket) and experimental (parenthesis) values of other authors are also presented [36]. The calculated values of HI are compared with experimental Vickers hardnesses (HV).

Phase ρ B G E ν HI
(g/cm3) (GPa) (GPa) (GPa) (GPa)

c-Al4Mg4B56 2.717 200.5 191.6 435.9 0.14 28.3

{199.6} {191.5} {435.3} {0.14} {27.6}
c-Al3Mg3B56 2.598 199.1 172.2 401.0 0.16 25.4
(27–28)
c-Mg4C8B48 3.038 227.6 215.8 491.9 0.14 31.8
{228.2} {217.0} {494.4} {0.14} {31.4}
(26–33.8)
a-Al4Mg4B56 2.589 163.0 106.6 262.5 0.23 15.7
a-Al3Mg3B56 2.565 179.9 118.4 291.3 0.23 17.5
a-e-Al3Mg3B56 2.387 154.8 92.6 231.6 0.25 13.7
a-c-Al3Mg3B56 2.770 216.6 132.8 330.8 0.25 19.6
170 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171
Fig. 10. Calculated intrinsic hardness of the crystalline and amorphous BAM samples (cf.
Table 3) as a function of sample density (ρ).
film. According to our theoretical results, the hardness of the amor-
phous BAM materials increases with their density. Therefore one can
assume that an increase in film density with discharge power density
also can promote the strengthening of the films.
To explain an increase in the hardness of the amorphous films with
an incorporation of carbon (cf. Fig. 7) let us use the results presented in
Table 3 and Fig. 11. These results show that the elastic moduli, intrinsic
hardness and ideal shear strength of c-Mg4C8B48 (a BAM material with
interstitial carbon) are highest among the BAM structures considered
here. An incorporation of the carbon atoms in a BAM material can lead
to the formation of the strong C-B4 units (cf. Fig. 9a) that, in turn,
strengthen inter-icosahedron interactions. As a result, the strength of
the material will increase.
Fig. 11. Shear stress-strain relations for the crystalline BAM structures.
4. Conclusions
Three sets of Al-Mg-B-C films were deposited by DC magnetron
sputtering from the AlMgB14 and B4C targets at different discharge
power densities at the AlMgB14 (PBAM) and B4C (PB4C) targets:
PBAM = 1.2–4.6 W/cm2, PB4C = 0 (set A); PBAM = 1.1–4.1 W/cm2,
PB4C = 1.0 W/cm2 (set B); PB4C = 0–3.4 W/cm2, PBAM = 4.1 W/cm2
(set C). The deposited films were characterized by atomic force micros-
copy, X-ray diffraction, transmission electron microscopy, Fourier trans-
form infrared spectroscopy, X-ray photoelectron spectroscopy,
nanoindentation, and scratch testing. All the deposited films are X-ray
amorphous. The roughness of the films surfaces increases with dis-
charge power densities at both targets. In the low-powered films, the
B\\O, Al\\O, Mg\\O, B\\B and Al\\B bonds were detected. The B\\B,
Al\\B and Mg\\O bonds strengthen, and the B\\O bonds weaken,
when PBAM and PB4C increase. An increase of PB4C also promotes a
strengthening of C\\C and C\\B bonds. The low-powered films exhibit
low hardness due to the predominance of weak B\\O bonds. Both the
nanohardness and elastic modulus increase with discharge power den-
sities up to 30.2 GPa and 304 GPa, respectively. Both experimental and
theoretical investigations enable one to suppose that the observed hard-
ness enhancement is due to the formation of the icosahedral B\\B net-
work and film densification. An introduction of carbon leads to the
formation of the strong C-B4 units that strengthen Al-Mg-B-C films.
The critical load of delamination increases with PBAM and decreases
with an increase in PB4C. The films exhibit a coefficient of friction in
the range of 0.09–0.2.
Acknowledgements
This work was supported by the STCU Contract No. 5964. We would
like to thank Stan Veprek for his comments on the mechanisms of the
strength enhancement in BAM-based films. We are grateful to Dr. O.
Lytvyn for AFM measurements, Dr. O.K. Sinelnichenko for XPS measure-
ments and PhD V.F. Brytun for TEM investigations. The authors are
grateful to the directorate of the Summery Institute at Jackson State
University for the possibility to perform large-scale calculations.
References
[1] W. Higashi, T. Ito, Refinement of the structure of AlMgB14, J. Less Common Met. 92
(1983) 239–246.
[2] B.A. Cook, J.L. Harringa, T.L. Lewis, A.M. Russell, Y. Lee, Processing studies and select-
ed properties of ultra-hard AlMgB14, J. Adv. Mater. 36 (3) (2004) 56–63.
[3] A. Ahmed, S. Bahadur, B.A. Cook, J. Peters, Mechanical properties and scratch test
studies of new ultra-hard AlMgB14 modified by TiB2, Tribol. Int. 39 (2006) 129–131.
[4] X. Jiang, J. Zhao, A. Wu, Y. Bai, X. Jiang, Mechanical and electronic properties of B12-
based ternary crystals of orthorhombic phase, J. Phys.: Condens. Matter 22 (2010)
315503–315508.
[5] V.I. Ivashchenko, P.L. Scrynskyy, S.N. Dub, O.O. Butenko, A.O. Kozak, O.K.
Sinelnichenko, Structural and mechanical properties of Al―Mg―B films: Experi-
mental study and first-principles calculations, Thin Solid Films 599 (2016) 72–77.
[6] Y. Tian, M. Womack, P. Molian, C.C. Lo, J.W. Andregg, A.M. Russell, Microstructure
and nanomechanical properties of Al-Mg-B-Ti films synthesized by pulse laser de-
position, Thin Solid Films 418 (2002) 129–135.
[7] Y. Tian, A.F. Bastawros, C.C.H. Lo, A.P. Constant, A.M. Russell, B.A. Cook, Superhard
self-lubricating AlMgB14 films for microelectromechanical devices, Appl. Phys. Lett.
83 (2003) 2781–2783.
[8] Y. Tian, G. Li, J. Shinar, N.L. Wang, B.A. Cook, J.W. Anderegg, A.P. Constant, A.M.
Russell, J.E. Snyder, Electric transport in amorphous semiconducting AlMB14 films,
Appl. Phys. Lett. 85 (2004) 1181–1183.
[9] Z. Wu, Y. Bai, W. Qu, A. Wu, D. Zhang, J. Zhao, X. Jiang, Al-Mg-B thin films prepared
by magnetron sputtering, Vacuum 85 (2010) 541–545.
[10] C. Yan, Z.F. Zhou, Y.M. Chohg, C.P. Liu, Z.T. Liu, K.Y. Li, I. Bello, O. Kutsay, Synthesis
and characterization of hard ternary AlMgB composite films prepared by sputter de-
position, Thin Solid Films 518 (2010) 5372–5377.
[11] B.A. Cook, J.L. Harringa, J. Anderegg, A.M. Russell, J. Qu, P.J. Blan, C. Higdon, A.A.
Elmoursi, Analysis of wear mechanisms in low-friction AlMgB14–TiB2coatings,
Surf. Coat. Technol. 205 (2010) 2296–3001.
[12] W. Liu, Q.-S. Meng, Y. Miao, F.-H. Chen, L.F. Hu, Preparation and Characterization of
AlMg-B thin films by magnetron sputtering, Adv. Mater. Res. 465 (2012) 112–117.
[13] J. Hay, P. Agee, E. Herbert, Continuous stiffness measurement during instrumented
indentation testing, Exp. Tech. 3 (2010) 86–94.
 V.I. Ivashchenko et al. / Surface & Coatings Technology 309 (2017) 164–171
[14] R.T. Downs, M. Hall-Wallace, The American Mineralogist Crystal Structure Database,
American Mineralogist 88 (2003) 247–250.
[15] P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car, C. Cavazzoni, D. Ceresoli, G.L.
Chiarotti, M. Cococcioni, I. Dabo, A.D. Corso, S. de Gironcoli, S. Fabris, G. Fratesi, R.
Gebauer, U. Gerstmann, C. Gougoussis, A. Kokalj, M. Lazzeri, L. Martin-Samos, N.
Marzari, F. Mauri, R. Mazzarello, S. Paolini, A. Pasquarello, L. Paulatto, C. Sbraccia, S.
Scandolo, G. Sclauzero, A.P. Seitsonen, A. Smogunov, P. Umari, R.M. Wentzcovitch,
Quantum espresso: a modular and open-source software project for quantum simu-
lations of materials, J. Phys.: Cond. Matter 21 (2009) 395502–395519.
[16] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made
Simple, Phys. Rev. Lett. 77 (1996) 3865–3868.
[17] D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue for-
malism, Phys. Rev. B 41 (1990) 7892–7895.
[18] S.R. Billeter, A. Curioni, W. Andreoni, Efficient linear scaling geometry optimization
and transition-state search for direct wavefunction optimization schemes in density
functional theory using a plane-wave basis, Comput. Mater. Sci. 27 (2003) 437–445.
[19] H.J. Monkhorst, J.D. Pack, Special points for Brillonin-zone integrations, Phys. Rev. B
13 (1976) 5188–5192.
[20] V.I. Ivashchenko, V.I. Shevchenko, P.E.A. Turchi, First-principles study of the atomic
and electronic structures of crystalline and amorphous B4C, Phys. Rev. B 80 (2009)
235208–235209.
[21] R. Golesorkhtabar, P. Pavone, J. Spitaler, P. Pusching, C. Draxl, Elastic: a tool for cal-
culating second-order elastic constants from first-principles, Comput. Phys.
Commun. 184 (2013) 1861–1873.
[22] X. Jiang, J. Zhao, X. Jiang, Correlation between hardness and elastic moduli of the co-
valent crystals, Comput. Mater. Sci. 50 (2011) 2287–2290.
[23] P. Pascuta, G. Borodi, M. Bosca, L. Pop, S. Rada, E. Culea, Preparation and structural
characterization of some Fe2O3-B2O3-ZnO glasses and glass ceramics, J. Phys.:
Conf. Ser. 182 (2009) 012072–012074.
[24] D. Music, J.M. Schneider, V. Kugler, S. Nakao, P. Jin, M.O. Stblom, L. Hultman, U.
Helmersson, Synthesis and mechanical properties of boron suboxide thin films, J.
Vac. Sci. Technol. A 20 (2002) 335–337.
[25] D. Ghosh, G. Subhasha, C.H. Lee, Y.K. Yap, Strain-induced formation of carbon and
boron clusters in boron carbide during dynamic indentation, Appl. Phys. Lett. 91
(2007) 061910.
[26] A.C. Ferrari, S.E. Rodil, J. Robertson, Interpretation of infrared and Raman spectra of
amorphous carbon nitrides, Phys. Rev. B 67 (2013) 155306–155320.
171
[27] A. Nylund, I. Olefjord, Hydration of A12O3 and decomposition of Al(OH)3 in a Vacuum
as Studied by ESCA, Surf. Interface Anal. 21 (1994) 283–289.
[28] B.R. Strohmeier, Magnesium Aluminate (MgAl2O4) by XPS, Surf. Sci. Spectra 3
(1994) 121–127.
[29] A. Talapatra, S.K. Bandyopadhyay, P. Sen, P. Barat, M. Mukherjee, X-ray photoelec-
tron spectroscopy studies of MgB2 for valence states of Mg, Phys. C 419 (2005)
141–147.
[30] C. Higdon, B. Cook, J. Harringa, A. Russell, J. Goldsmith, J. Qu, P. Blau, Friction and
wear mechanisms in AlMgB14-TiB2 nanocoatings, Wear 271 (2011) 2111–2115.
[31] D. Music, F. Hensling, T. Pazur, J. Bednarcik, M. Hans, V. Schnabel, C. Hostert, J.M.
Schneider, Bonding and elastic properties of amorphous AlYB14, Sol. St. Comun.
169 (2013) 6–9.
[32] S. Li, B. Zeng, Z. Feng, Y. Liu, W. Yang, L. Cheng, L. Zhang, Effects of heat treatment on
the microstructure of amorphous boron carbide coating deposited on graphite sub-
strates by chemical vapor deposition, Thin Solid Films 519 (2010) 251–258.
[33] J.F. Ducel, J.J. Videau, D. Gonbeau, G. Pfilstergullouzo, X-ray photoelectron spectra of
sodium borophosphate glasses, Phys. Chem. Glas. 36 (1995) 247–252.
[34] J.S. Corneille, J.-W. He, D.W. Goodman, XPS characterization of ultra-thin MgO films
on a Mo(100) surface, Surf. Sci. 306 (1994) 269–278.
[35] L. Rosenberger, R. Baird, E. McCullen, G. Auner, XPS analysis of aluminum nitride
films deposited by plasma source molecular beam epitaxy, Surf. Interf. Anal. 40
(2008) 1254–1261.
[36] H. Kolpin, D. Music, G. Henkelman, J.M. Schneider, Phase stability and elastic properties
of XMgB14 sudied by ab initio calculations (X = Al,Ge,Si,C,Mg,Sc,Ti,V,Zr,Nb,Ta,Hf), Phys.
Rev. B 78 (2008) 054122–054126.
[37] D. Music, U. Kreissig, Z.S. Czigany, U. Helmersson, J.M. Schneider, Elastic modulus-
density relationship for amorphous boron suboxide thin films, Appl. Phys. A 76
(2003) 269–271.
[38] R.F. Zhang, S. Veprek, A.S. Argon, Anisotropic ideal strengths and chemical bonding of
wurtize BN in comparison to zincblende BN, Phys. Rev. B 77 (2008) 172103–172104.
[39] R.F. Zhang, S. Veprek, A.S. Argon, Effect of nanometer-sized grains on superhardness
of c-BC5: a first-principles study, Phys. Rev. B 80 (2009) 233401–233404.
[40] S. Veprek, Recent search for new superhard materials: Go nano! J. Vac. Sci. Technol.
A 31 (2013) 050822–050833.