3028 IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 44, NO.

12, DECEMBER 2016

Magnetron Sputtering System for Deposition of

Multinanolayered Coatings With Reactive Gas
Activation in Microwave Discharge
A. I. Kuzmichev, Senior Member, IEEE, V. I. Ivashchenko, V. V. Perevertailo, and P. L. Skrynskyi

Abstract— The design of a dual gas magnetron system for ion

sputtering of two source materials with an activation of a reactive
gas in the remote microwave (MW) discharge for the deposition of
multinanolayered coatings is presented. The design of the reactive
gas activator with the electron cyclotron resonance was realized
on the basis of the analysis of possible schemes for the formation
of MW gas discharge plasma systems. The vacuum electron
magnetron is used as a MW generator (2.45 GHz and ∼800 W).
Geometry of the electrodynamic part of the activator was selected
by means of simulation with Comsol Multiphysics. The practical
examination of the dual sputtering system was carried out by
sputtering of Ti and B4 C targets, while nitrogen was used as Fig. 1. Design of MW reactive gas activator (its working position is vertical).
the reactive gas. The characteristics of the multinanolayered 1—plunger. 2—waveguide. 3—MW vacuum magnetron 2M214. 4—quartz
Ti-B-C-N coatings were studied and it was determined that the glass window. 5—discharge chamber. 6—outlet grid. 7—solenoid. 8—PTFE
deposited coatings had the nc-TiN x /(a-BN+a-C) structure. The insert. Magnetron 2M214 is not shown in the right view.
Knoop hardness of the coatings was found to be ∼45 GPa, while
the nanohardness was lower than Knoop ones by ∼20%–30%. gas can be enhanced by exciting and ionizing the reactive
The presented sputtering system could be recommended for gas molecules either in the electric discharge or under ultra-
deposition of wear-resistant and protective coatings. violet irradiation. The activation of the reactive gas may also
Index Terms— Coating, magnetrons, plasma-material- decrease the lower limit of the working gas pressure and the
processing applications, sputtering.
cross-contamination of one magnetron target with sputtered
I. I NTRODUCTION material from the other target. In this paper, we describe a new
microwave (MW) plasma discharge activator of reactive gas

T HE ion sputtering in low-pressure magnetron discharge

allows sputtering of any material and perform the process
in any gas atmosphere for the deposition of oxides, nitrides,
carbides, and their combinations [1]. Having a number of
advantages, this method successfully competes with such
industrial technologies as electron beam evaporation and
chemical vapor deposition with ion-plasma assistance. The
combination of several sputtering sources with different tar-
gets [2]–[10] and the alternation of their switch-ON/switch-OFF
modes allows the deposition of multinanolayered coatings
with different composition of individual nanolayers. However,
the difference in the chemical interaction of the reactive gas
with different target materials raises the problem for the
stoichiometric deposition of different nanolayer material.
To solve this problem, the chemical activity of the reactive
Manuscript received July 18, 2016; revised September 2, 2016; accepted
September 6, 2016. Date of publication September 26, 2016; date of current
version December 16, 2016. This work was supported by STCU under
Contract 5964.
A. I. Kuzmichev and V. V. Perevertailo are with the Kiev Polytechnic
Institute, National Technical University of Ukraine, 03056 Kiev, Ukraine
(e-mail: a.kuzmichev@edd.ntu-kpi.kiev.ua; vladimir_mj@ukr.net).
V. I. Ivashchenko and P. L. Skrynskyi are with the Frantsevich Institute for
Problems of Materials Science, National Academy of Sciences of Ukraine,
03142 Kiev, Ukraine (e-mail: ivash@ipms.kiev.ua; petro@ipms.kiev.ua).
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TPS.2016.2607285
0093-3813 © 2016 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
and its employment for a dual magnetron sputtering system.
The advantages of such type of activator are high density of
generated plasma at low gas pressure and possibility to work
without electrodes, which could be destroyed through reaction
with the chemically active gas.
II. D ESIGN AND PARAMETERS OF E LECTRODELESS
M ICROWAVE P LASMA ACTIVATOR OF R EACTIVE G AS
There are various approaches for building MW reactive gas
activators for magnetron sputtering systems [11]–[15]. The
activators may be classified as those with MW plasma removed
from sputtering argon discharge plasma or with one common
plasma generated near the sputtering target simultaneously
due to energy from MW source and sputtering power source.
Taking into account the advantages and the disadvantages
of the known engineering solutions, the MW activator of
resonator type with remote plasma has been selected as a rela-
tively simple suitable variant. The electron cyclotron resonance
(ECR) mode of the MW plasma discharge has been used, since
it provides high level of gas ionization at low working gas
pressures comparable with ones of magnetron sputtering dis-
charge [13]–[15]. As it is known, the high-frequency electric
field is to be orthogonal to the static magnetic field at the ECR
mode. Based on this, the MW electrodeless activator has been
designed and fabricated as it is shown in Fig. 1. The vacuum

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 KUZMICHEV et al.: MAGNETRON SPUTTERING SYSTEM FOR DEPOSITION OF MULTINANOLAYERED COATINGS
Fig. 2. Electric field distribution in the MW activator. (a) PTFE insert is
absent (H113 wave). (b) PTFE insert is present (H114 wave).
electron magnetron of 2M214 type is employed for the MW
power generation ( f = 2.45 GHz and W ∼ 800 W). Note, the
magnetron 2M214 is intended for use in domestic MW ovens.
In the cylindrical waveguide 2, the magnetron 2M214
excites the wave of H11 type propagating toward the discharge
chamber 5, which is supplied with a reactive gas (oxygen and
nitrogen). Plasma species from the discharge chamber go out
into a deposition chamber (not shown in the figure) through the
holes of the outlet grid 6. Controlling the current of solenoid 7,
it allows to regulate the operating mode of gas ionization and
activation. The degree of gas ionization, which is used as a
measure of gas activation, is determined by the value of current
to an ion collector. The collector (not shown in the figure)
is located in the deposition chamber under the outlet grid 6.
The plunger 1 is used for tuning the resonance. Cooling of
the magnetron 2M214 is due to air blowing, cooling of the
solenoid 7 is due to water cooling, and other parts are cooled
by passive air cooling.
The choice of the geometry and the dimensions of the
MW electrodynamic part of the activator was performed by
means of 3-D simulation in Comsol Multiphysics [16]. In the
activator, the resonator mode of high-frequency oscillations
is sustained with the transmission of MW power from the
magnetron 2M214 (from the magnetron pin antenna) to gas
plasma discharge in the discharge chamber 5 through the
quartz glass window 4.
In Fig. 2, the electric field distribution is shown in the
resonator of the optimum geometry before the initiation of
the MW discharge.
One can see the standing waves of the H113 type or the
H114 type existing in the resonator, consisting from the cylin-
drical waveguide 2, quartz glass window 4, and the discharge
chamber 5. In Fig. 2(a), the case of the H113 wave without
an additional dielectric polytetrafluorethylene (PTFE) insert
within the discharge chamber is shown. In Fig. 2(b), the case
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3029
Fig. 3. Dual magnetron sputtering system with MW activator of reactive
gas: CS—programmable CS. M1 and M2—sputtering magnetrons (targets
are shown by bold lines). PS1 and PS2—power supplies for sputtering
magnetrons. PSsub —negative substrate bias supplier. S1 and S2—shutters.
Sub—substrate. TC—thermocouple. The location (projection) of the outlet
grid of the gas activator is shown by dashed-dotted line. Magnetic force lines
above the magnetron targets are shown by thin lines.
of the H114 wave with the PTFE insert disposed at the front
of the discharge chamber (near the window 4) is shown. The
diameter of the PTFE insert equals to the inner diameter of
the discharge chamber 5. The thickness (the length along the
axis) of the insert is of such value that one end of the insert
is pressed to the window 4 and the second end is located
in the cross-sectional plane of the solenoid 7 with maximum
magnetic field (that is at the mid-height of the solenoid).
Thus, the PTFE insert pushes away the gas from the left
side (in Fig. 1) of the discharge chamber 5. Therefore, the
interaction of the electromagnetic wave with the reactive gas
begins at the location of the maximum magnetic field, and
then, it continues in the decreasing magnetic field. This design
facilitates the penetration of the electromagnetic waves into
the MW discharge plasma due to helicon surface wave excita-
tion [13]. Moreover, the decreasing magnetic field creates an
electromagnetic force pushing the gas plasma together with its
active species toward the region of weaker field, i.e., toward
the outlet grid 6.
III. M AGNETRON S PUTTERING S YSTEM W ITH MW
ACTIVATOR OF R EACTIVE G AS
Fig. 3 shows the combination of the MW reactive gas
activator with two sputtering magnetrons. The sputtering
magnetrons (M1 and M2) are alternately (or simultaneously)
supplied from two power sources (PS1 and PS2, respectively).
Various magnetron power supply modes may be used with:
(1) direct current voltage; (2) mid-frequency (or pulse-
modulated) voltage in kilohertz range (22–880 kHz); (3) radio
frequency voltage in megahertz range (13.56 MHz). The power
supplies PS1 and PS2 (powered up to 500 W) are controlled
by the programmable control system (CS), which provides
the desired sequence and duration of working (sputtering)
periods as well as the values of sputtering discharge power of
each sputtering magnetron for the deposition of coatings with
 3030
different structures (multilayered, gradient, and so on). When
the sputtering magnetrons work alternatively, which could
make up the pauses of sputtering discharges, the delays of
arising the discharges after the pauses may occur. In order
to exclude the delays after pauses (when one sputtering
magnetron is switched-OFF and the other magnetron is to
be switched-ON), auxiliary low-current (20–50 mA) nonsput-
tering dc discharges are maintained in each magnetron. The
substrate holder is also provided with a thermocouple for
measuring the substrate temperature and the power supplier
PSsub for a negative bias voltage to the substrate.
The microprocessor-based programmable CS regulates and
modulates the electrical power supply of the magnetrons and
of the gas inflow activator as well as the value of the negative
substrate bias accordingly to a technological program. It also
controls the position of shutters and parameters of other parts
of the dual sputtering system.
IV. E XAMINATION OF THE D UAL M AGNETRON
S PUTTERING S YSTEM W ITH R EACTIVE G AS
ACTIVATION . R ESULT AND D ISCUSSION
The test of the developed dual magnetron sputtering system
demonstrated that it is stably operated for long time. The
density of the ion current to the collector at the distance
of 10 cm from the outlet grid was several milliamperes per
square centimeter with using nitrogen as the reactive gas at
pressure of 0.1–1.5 Pa. The control of the ion current was
carried out by changing the current of the solenoid and the
operation mode of the MW generator. Total examination of
the dual magnetron sputtering system with gas activation was
examined in the process of sputtering Ti and B4 C targets
and the deposition of multinanolayered Ti-B-C-N (TiN/BCN)
coatings onto monocrystalline silicon substrates. The struc-
ture, chemical composition, and mechanical properties were
investigated at different process deposition conditions [17].
In this paper, the sputtering currents were 200 mA for Ti
target and 100 mA for B4 C target, the substrate temperature
was 350 °C. The negative substrate bias was −50 V, the
N2 flow values were 4–20 sccm, and the total gas flow of
Ar + N2 was 20–80 sccm at working gas pressure in the depo-
sition chamber ∼0.15 Pa. The multinanolayered Ti–B–C–N
coatings consisted of 58 paired layers of TiN and BCN with
total coating thickness of ∼0.5 µm.
The measurements demonstrated the following struc-
ture of multinanolayered nc-TiNx /(a-BN+a-C) coatings: the
Ti–B–C–N coatings consist of nanocrystalline TiNx layers and
amorphous hexagonallike BN layers with the inclusions of
amorphous sp2 carbon. Otherwise speaking, TiNx nanocrys-
tallites (3.4–6.5 nm) are embedded into the amorphous matrix
consisting of the mixture of boron nitride (a-BN) and amor-
phous carbon (a-C). The hardness and elastic modulus of
the multinanolayered Ti–B–C–N coatings were compared with
published data and it was confirmed that the a-C phase in the
amorphous BN layer improves their mechanical properties.
Depending on deposition conditions, the nanohardness and
elastic modulus ranges within 8–35 GPa and 100–420 GPa,
respectively. Scratch tests showed that adhesion between the
multinanolayered coatings and substrate is higher for coatings
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IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 44, NO. 12, DECEMBER 2016
with thicker amorphous layers. The friction coefficient of the
nanolayered coatings changes insignificantly and is about 0.1
for all samples. The optimum multinanolayered structure with
amorphous a-BCN layers formed in titanium nitride coatings
increases the nanohardness from 25 to 35 GPa and Knoop
hardness from 35 to 52 GPa. The strengthening of our nanolay-
ered coatings is similar to that of other nanocomposites, which
is caused by the prevention of the movement of dislocations
by the amorphous layer [18].
V. C ONCLUSION
The dual magnetron sputtering system for the deposition
of nanolayered coatings with the reactive gas activation in
the remote MW discharge has been designed. The system
provides alternating sputtering of two different targets and
the deposition of multinanolayered coatings. The vacuum
electron magnetron is employed as the MW generator to
support electrodeless electrical discharge in the gas activator
of the resonator type. The designed magnetron sputtering
system has been successfully tested during the deposition of
multinanolayered TiN/BCN coatings. The deposited coatings
have structures consisting of nanocrystalline TiNx layers and
amorphous hexagonallike BN layers with the inclusions of
amorphous sp2 carbon. The a-C phase in the amorphous BN
layer improves the mechanical properties of the coatings: the
nanohardness increases up to 35 GPa and Knoop hardness up
to 52 GPa. The multinanolayered (nanocomposite) Ti–B–C–N
coatings deposited at comparatively low substrate tempera-
tures (∼350 °C) could be recommended for employing as
wear-resistant and protective coatings.
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