Thin Solid Films 475 (2005) 208 – 218

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Reactive magnetron sputtering of thin films: present status and trends

J. Musila,b,*, P. Barocha, J. Vlčeka, K.H. Namc, J.G. Hanc
a
Department of Physics, University of West Bohemia, Univerzitnı́ 22, 306 14 Plzeň, Czech Republic
b
Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, 182 21 Praha 8, Czech Republic
c
Center for Advanced Plasma Surface Technology, SungKyunKwan University 300 Chunchun-Dong, Jangan Gu, Suwon 440-746, South Korea

Available online 15 September 2004

Abstract

This paper gives a critical review of the present state of the knowledge in the field of dc reactive magnetron sputtering of compound films.
It analyses (i) the hysteresis effect and the methods of its elimination, (ii) problem of stability of reactive sputtering and (iii) deposition of
transparent oxides in the transition mode of sputtering. It shows the conditions under which oxides are reactively sputtered with high
deposition rates a D oxide achieving up to approximately 77% of that of a pure metal a D Me, i.e. a D oxide/a D Mec0.77. A special attention is
devoted to the elimination of arcing in sputtering of insulating films using pulsed dual magnetron or sputtering of oxides from a
substoichiometric target. Also, the ion bombardment of films growing on insulating or unbiased substrates in dc pulsed magnetron sputtering
is discussed in detail. As an example, a new possibility to form superhard single-phase films based on solid solutions using dc reactive
magnetron sputtering is shown. At the end, future trends in dc reactive magnetron sputtering are outlined.
D 2004 Elsevier B.V. All rights reserved.

Keywords: DC continuous and pulsed reactive magnetron sputtering; Compounds; Deposition rate; Nanocomposites; Film properties

1. Introduction instance, Ti changes to TiN or TiO2 when nitrogen or

Since approximately 1980, a reactive sputtering of thin
films is intensively investigated because the sputtering of
metallic targets in the presence of reactive gas (RG) makes it
possible to easily form compound films, such as nitrides,
oxides, carbides or their combinations. The reactive sputter-
ing process can be, according to the amount of RG used in
the film deposition, divided into three modes: (a) metallic,
(b) transition and (c) reactive. A typical characteristic of the
reactive magnetron sputtering is a low deposition rate of
compounds a D com produced in the reactive mode compared
to that of the pure metallic or alloyed films a D Me produced in
the metallic mode (see Fig. 1a). The ratio a D Me/a D com is
relatively small (3–4) for nitrides but achieves high (10–15)
values for oxides.
The decrease in a D of films sputtered in the reactive
mode is due to a reaction of the RG with the surface of the
sputtered target and its conversion to a compound, for
* Corresponding author. Tel.: +42 37 763 2200; fax: +42 37 763 2202.
E-mail address: musil@kfy.zcu.cz (J. Musil).
0040-6090/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2004.07.041
oxygen is used as RG. This results in (1) decrease of (i)
sputtering yield (c MeNc com, e.g. c TiNc TiN) and (ii) magnet-
ron discharge voltage U d and (2) rise of the hysteresis
effect (see Fig. 1b). The decrease in a D strongly depends
particularly on the material of the sputtered target and the
kind of RG. The electrical conductivity of the sputtered
target after its reaction with RG is also important. When
the reaction product is electrically insulated, two further
problems occur: (1) non-sputtered surfaces of the target
(very significant in planar magnetrons) are covered by
thick dielectric layers, which are charged up, and cause an
arcing when the charge achieves a threshold value; and (2)
the anode of the magnetron disappears also due to its
dielectric layer cover.
From this short survey, it is seen that there are three main
limitations of the reactive sputtering: (1) hysteresis effect,
(2) jump transition from the metallic to the reactive mode of
sputtering, which exclude to produce compound films in a
certain interval of their stoichiometry x defined, for
instance, as x=N/Ti for the TiNx film, and (3) arcing and
bdisappearing anodeQ, when dielectric films are sputtered. In
 J. Musil et al. / Thin Solid Films 475 (2005) 208–218
Fig. 1. Schematic illustration of (a) deposition rate, a D, of sputtered films,
and (b) partial pressure of RG, p RG as a function of flow rate of RG, / RG.
recent years, some of these limitations were already
successfully overcome as reported by excellent review
articles [1–20]. This paper reviews the present state-of-the-
art in the high-rate reactive magnetron sputtering of
compound films with prescribed stoichiometry and elimi-
nation of arcing when deposited films are dielectric. A
special attention is devoted to reactive magnetron sputtering
of nanocomposite coatings composed of a mixture of very
fine grains of different crystallographic orientations. The
formation of ionized atoms of sputtered material during dc
pulse sputtering at high (N500 W/cm2) target power
densities is also briefly given.
2. Hysteresis effect
Many problems encountered in the preparation of non-
stoichiometric compound films by reactive sputtering are
due to a hysteresis effect (see Fig. 1). This effect arises in
consequence of two competitive processes: (1) the sputter-
ing of the target surface and (2) the covering of its surface
by reaction products. Fig. 1b illustrates the dependence of
RG partial pressure, p RG, as a function of the flow rate,
/ RG, of the RG supplied into the deposition chamber with
and without discharge. The hysteresis occurs in the presence
of discharge only.
209
At low values of the RG flow rate / RG (interval AB), all
RG is gettered by the sputtered metal. At point B, the flow
rate / RG(B) into the chamber is equal to the gettering rate of
sputtered metal. Every small increase in / RG results in a
sudden (1) increase of p RG in the deposition chamber and
(2) decrease of the film deposition rate a D. A further
increase of / RG (interval CD) results in a linear increase of
p RG and almost constant a D, which is typical for reactive
mode of sputtering. The decrease of / RG from D to E is
accompanied by decrease of p RG, but a return to the metallic
mode (interval EC) is delayed. This is because p RG remains
high until a compound layer on the surface of the sputtered
target is fully removed and metal is again exposed to be
sputtered. As a result, the consumption of RG increases and
p RG decreases to the background level. A closed hysteresis
loop is formed in this way.
The hysteresis is an undesirable phenomenon because it
(1) prevents to form MeRG x compound films with
stoichiometry x corresponding to p RG in the interval BC;
here Me=Ti, Cr, Zr, etc., and RG=N, O, C, B, etc., and (2) is
responsible for unstable sputtering at / RG in a close vicinity
of the transition from BC. Therefore, a considerable effort
has been devoted to find means for its elimination. First, it
was suggested by Maniv et al. [21] to introduce a baffle
between the substrate and the target with Ar inlet into the
baffle and RG inlet into the system on the substrate side.
However, this modified magnetron system called bbaffledQ
magnetron suffers from three principal drawbacks: (1)
frequent cleaning of the baffle grid, (2) reduction of the
metal flux to the substrate through grid and (3) reduction of
plasma bombardment of the growing film if the baffle is
grounded. Despite those, the last problem may be solved by
either placing a positively biased electrode in the substrate
region to pull out the plasma from the baffle, or by biasing
the substrate. This solution is not, however, suitable for an
industrial production. For this purpose, simple systems with
no obstacles, such as the baffles or grids, between the
sputtered target and the substrate, are needed. It requires
either fully eliminating the hysteresis effect or ensuring a
stable sputtering in the transition mode. These requirements
meet sputtering systems with a pumping speed S larger than
a critical pumping speed, S c [22–24], sputtering systems
controlled by plasma emission monitoring (PEM) [25,26] or
gas pulsing [27,28], dual magnetrons [12,29], magnetrons
with a full target erosion [30–33], magnetrons equipped
with substoichiometric ceramic targets [34], and recently
developed advanced closed field dual target sputtering
systems without magnetron racetrack.
3. Elimination of hysteresis with a high pumping speed
of the pumping system
A condition necessary for the elimination of the
hysteresis effect can be derived from an equilibrium state
between the gettering of RG by sputtered material and the
210 J. Musil et al. / Thin Solid Films 475 (2005) 208–218
removal of RG from the deposition chamber by the
pumping system [22],
URG ¼ pRG SRG þ sURG
where S RG is the pumping speed of the pumping system for
the RG and s/ RG is the flow rate of RG gettered by
sputtered material. The hysteresis effect occurs if the system
is unstable. It was found that the solution of Eq. (1) is stable
under the following condition,


SRG NSc ¼  BsURG =BpRG Þmax ð2Þ
where S c is the critical pumping speed of the pumping
system. This means that the hysteresis effect can be
eliminated if the pumping speed S RG of the pumping
system is greater than a critical value of S c given by Eq. (2).
A possibility to remove the hysteresis effect is schemati-
cally shown in Fig. 2. Here, the dependences s/ RG=f( p RG)
and / RG=f( p RG) for S RGbS c and S RGNS c are given. In the
case of S RGNS c, the hysteresis effect can be eliminated even
despite the fact that the derivative Bs/ RG/Bp RG is negative
because the dependence / RG=f( p RG) is an unambiguous
function. To every value of / RG corresponds only one value
of p RG. The validity of this conclusion was verified
experimentally for the case of reactive dc magnetron
sputtering of titanium nitride films [23,24].
The main problem with increasing the pumping speed
lies in the considerably added costs at the building stage of
new machines. Despite this fact, a new generation of high
speed diffusion pumped coaters with 6500 l/s diffusion
pumps was put into operation in the mid-1990s by Von
Ardenne Coating Technology (then BOC Coating Technol-
Fig. 2. Schematic illustration of / RG as a function of p RG in sputtering system with (S RG1bS c) and without (S RG1NS c) the hysteresis effect. The dependence of
the flow of RG gettered by sputtered target material s/ RG as a function of p RG is also given.
ogy) and recently advanced turbomolecular coaters with
four 1000–2000 l/s turbomolecular pumps surrounding each
magnetron position (Von Ardenne Anlagentechnik b780
ð1Þ
mmQ) were developed [20]. This demonstrates a clear trend
to enhance pumping speeds of new coaters with the aim to
eliminate the hysteresis loop via an increase in S c.
4. Sputtering of compound films in the transition mode
The analysis given above shows that a stable deposition
of compound films in the transition mode of sputtering can
be realized when S RGNS c. However, in most sputtering
systems, particularly in industrial ones, the condition
S RGNS c is not satisfied and so the hysteresis effect takes
place. In such systems, a jump in p RG from point B to point
C occurs (Fig. 1) and in this interval of p RG (usually called
the bforbiddenQ interval) compound films cannot be
sputtered. This means that the formation of MeRGx films
in a certain interval of their stoichiometry x is not possible.
Experiments, however, show that just in this forbidden
interval of p RG not only stoichiometric films with x=1 but
also substoichiometric films (xV1) with new interesting
properties can be formed. Moreover, these stoichiometric
films (x=1) formed in the transition mode of sputtering are
deposited at a considerably higher deposition rate a D
compared to that of the stoichiometric film (x=1) sputtered
in the reactive mode of sputtering. These are main reasons
why special systems, which ensure a stable reactive
sputtering in the transition mode, i.e. in each point along
the line BC in Fig. 1, were developed.
 J. Musil et al. / Thin Solid Films 475 (2005) 208–218
Fig. 3. The dependence p O2=f(/ O2) in the pulsed (asymmetric bi-polar
operation, f r=100 kHz, s=5 As) sputtering system in which reactive
sputtering of MgO films is controlled by / O2 at p T=0.5 Pa. Single
unbalanced magnetron with Mg target of 100 mm in diameter, I da=1.5 A
(19 mA/cm2) and the substrate at d s-t=100 mm.
4.1. Stability control systems
As can be seen from Fig. 1, in the flow control of the RG
any small increase of / RG above / RG(B) results in a jump
transition from the metallic to reactive mode of sputtering.
This transition is irreversible and is very sharp, particularly
for oxides (see, for instance, Fig. 3). The sputtering system
with the control of / RG only does not allow to sputter the
films in the transition mode of sputtering. For instance,
stoichiometric oxides can be prepared only in the reactive
(oxide) mode at very low deposition rates a D (see a
schematic illustration of a D=f(/ RG) given in Fig. 1).
The operation in the transition mode is possible if the
control of / RG is combined with a control of p RG. It can be
done by two ways: (1) by variation of / RG using a plasma
emission monitoring (PEM) [4,35–38] or (2) by variation of
/ Ar in very fine steps.
The control system with PEM, which ensures a stable
sputtering at a selected value of p RG lying on the line BC,
uses a very fast electronic feedback (see Fig. 4). The light
from the plasma above the sputtered target is introduced
Fig. 4. Schematic illustration of the plasma emission monitoring (PEM) system.
211
using an optical fibre into a monochromator. Here, the
requested line of emission, for instance, Ti (k=395.8 nm) if
TiO2 films are formed, is selected and introduced into a
photomultiplier, where it is converted into an electrical
signal, which is proportional to the density of corresponding
element (Ti) in the plasma. This signal is compared in the
PEM controller with a reference signal (corresponding to the
desired set-point) and their difference controls the fast
piezoelectric gas flow valve to admit/reduce the / RG to the
system until the magnitudes of both the set-point signal and
the input signal are equal.
The second system ensures a stable sputtering of
compound films in the transition mode by the control of
/ Ar at a constant total pressure p T =p Ar + p RG = const. If very
fine steps in reducing / Ar are used, any partial pressure p RG
along the line BC can be adjusted and a stable operation of
the control system is ensured. This is demonstrated by the
dependence p O2=f(/ O2) measured in reactive sputtering of
TiOx films (see Fig. 5a). The control system is unstable
when the partial pressure of RG p RG overpasses some
critical value, i.e. when a very high-rate sputtering is
realized (see Fig. 5b). In our experiments, a stable sputtering
of TiOx films in the transition mode was realized at the
target power densities Q=I daU d/SV30 W/cm2.
5. Deposition rate of transparent oxides in the transition
mode sputtering
Fig. 5a clearly shows that transparent oxides can be
formed already in the transition mode of sputtering. There-
fore, the deposition rate a D of these oxides is considerably
higher than that of oxides sputtered in the oxide mode of
sputtering. However, the magnitude a D of transparent oxides,
produced in transition mode, strongly depends on the
construction and geometrical arrangement of the sputtering
system used. A maximum a D max of transparent TiOxc2
oxides sputtered by a dual magnetron (a D max=31.5 nm/min at
I da1,2=1.5 A) is more than two times higher than that of the
films sputtered by the single magnetron (a D max=12.7 nm/min
212 J. Musil et al. / Thin Solid Films 475 (2005) 208–218
at I da=1.5 A) and, moreover, depends on a configuration
of the magnetic field B between magnetrons. When the
polarity of magnets of both magnetrons in the dual
magnetron is opposite, the magnetic field B between
magnetrons is closed and such system is called the dual
magnetron with closed B field. If the polarity is the same,
the magnetrons are magnetically separated by a mirror-like
distribution of B between magnetrons and such system is
called the dual magnetron with mirror B field. A higher
a D max is achieved by the dual magnetron with a closed B
Fig. 5. The dependence p O2=f(/ O2) in the pulsed (asymmetric bi-polar
operation, f r=100 kHz, s=5 As) sputtering system in which reactive
sputtering of TiOx films is controlled by / O2 at p T=0.5 Pa. Dual
unbalanced magnetron equipped with Ti targets of 50 mm in diameter,
I da1,2=1.5 A (W t=25.9 W/cm2) and 3 A (W t=50.4 W/cm2), respectively, and
the substrate at d s-t=100 mm.
Fig. 6. The dependence p O2=f(/ O2) for the dual magnetron with mirror B
field and p O2 control of RG. Magnetrons are equipped with Ti target of 50
mm in diameter, f r=100 kHz, s=5 As, I da=1.5 A, d s-t=100 mm and p T=0.5 Pa.
field between magnetrons compared to that with mirror B
field (compare Figs. 5a and 6).
5.1. Discharge of dual magnetron
A distribution of the discharge above the sputtered
targets of the dual magnetron depends on the magnetic
field B between magnetrons (see Fig. 7). In the case when B
field is closed (opposite polarity of magnets between
magnetrons), the discharge is confined between the sput-
tered targets (see Fig. 7a). On the contrary, in the dual
magnetron with mirror B field (the same polarity of
magnets), discharges of individual magnetrons are separated
and mutually repelled (see Fig. 7b). This results in the
deposition over a larger area for the latter case and so in the
formation of thinner films. Therefore, in sputtering using the
dual magnetron with mirror B field, the deposition rate of the
transparent oxide sputtered in the transition mode of
sputtering becomes lower (a D TiOx c2=26.5 nm/min) com-
pared to that produced with the dual magnetron with closed B
field (a D TiOxc2=31.5 nm/min).
6. Arcing in reactive sputtering of insulating films
Arcing in reactive magnetron sputtering of insulating
films occurs in consequence of charging of insulating layers
formed on uneroded areas of the sputtered target. There are
two ways to suppress or eliminate arcing: (1) to eliminate
uneroded areas and (2) to remove the accumulated charge
from insulated surfaces on the uneroded areas [35–38].
The existence of uneroded areas is an inherent property
of the planar magnetrons. They are formed everywhere
outside the magnetron racetrack, strongly decrease the
efficiency of the target utilization and thus decide on the
target lifetime. In principle, there are two ways to eliminate
uneroded areas: (1) to scan a magnetic circuit (magnets)
 J. Musil et al. / Thin Solid Films 475 (2005) 208–218 213

Fig. 7. Photos of the discharge of the dual magnetron with (a) closed B field (opposite polarity of magnets between magnetrons) and (b) mirror B field (the
same polarity of magnets between magnetrons). Process parameters: symmetric bi-polar operation, f r=100 kHz, s=5 As, I da=1.5 A (77 mA/cm2), d s-t=100 mm
and p T=p Ar=0.5 Pa.

under the planar target or (2) to use a rotated cylindrical When the cathode voltage U d is negative, the target material
target. During a scanning of the magnetic circuit under the is sputtered. On the contrary, when U d is positive, the surface
target or a rotation of the cylindrical target above a stationary of the insulating layer on the uneroded areas is discharged as
magnetic circuit, the magnetron discharge bsweepsQ the a result of electron bombardment. Such a process is called
whole surface of the sputtered target. Therefore, in every bipolar pulsed magnetron sputtering. Arcing can be elimi-
moment, a certain part of the target is without a discharge and nated if the positive charge accumulated on the uneroded
reacts with the RG. This means that even these magnetrons, areas is discharged before reaching a critical value at which
which achieve almost a full target erosion, are covered by a the electric field across the insulating layer overpasses its
thin compound layer (MeRGx ), whose thickness depends on dielectric strength. This can be reached only in the case when
(i) a speed of scanning or rotation or (ii) reaction time of the the frequency of discharging f r is higher than a critical
RG with the sputtered metal. This thin (z10 nm) compound frequency f cr. The value of the critical frequency f cr can be
layer is, however, sufficient to change sputtering from metal estimated from the following formula [9,43].
to compound and so (i) to produce a hysteresis effect, for
instance, C-MAG with a full target erosion exhibits a fcr ¼ ðer e0 EB =Ji Þ1 ð3Þ
hysteresis effect [2], and (ii) arcing. where E B, e r, e 0 and J i are the dielectric strength of the
The hysteresis effect and arcing can be avoided only in insulating layer, the dielectric constant of this layer, the
the case when the whole surface of the sputtered target is
uninterruptedly exposed to the magnetron discharge and the
compound layer is continuously removed. To our knowl-
edge, only two sputtering sources meet such a requirement:
(1) rectangular magnetron with many racetracks oriented
perpendicularly to a larger side of the target, covering the
whole target surface along its length [32] and continuously
moving along its longer axis, i.e. the magnetron with an
endless one-way direction movement of many magnetic
circuits, producing many separated racetracks, under the
target [39] and (2) modified facing target sputtering systems.
At present, arcing in reactive sputtering can be reliably
and successfully eliminated when either a pulsed dual
magnetron or substoichiometric conductive target, for
instance, TiO2x , is used. Titanium dioxide films are now
intensively investigated due to their photocatalytic and self-
cleaning properties [40–42].

6.1. Pulsed dual magnetron

The principle of pulsed dual magnetron sputtering is

displayed in Fig. 8. The voltage polarity of magnetron Fig. 8. Schematic diagram of symmetric bi-polar pulsed dual magnetron
cathodes periodically changes from negative to positive. sputtering.
214 J. Musil et al. / Thin Solid Films 475 (2005) 208–218
permittivity of free space and the discharge current
density during a negative voltage pulse. Eq. (3) shows
that f cr is a function of the material to be sputtered. Therefore,
whereas no arcing is achieved for reactive sputtering of TiO2
at a pulsing frequency of 30 kHz, it takes a frequency
between 50 and 70 kHz for all arcing to disappear for Al2O3
[19].
6.2. Reactive sputtering of oxides using substoichiometric
target
Recently, Ohsaki et al. [34,44] proposed to use a
substoichiometric TiO2x target for a high-rate deposition
of TiO2 films instead of a pure Ti metal target. This
method has two advantages: (1) TiO2x material is an n-
type semiconductor having a sufficient electrical conduc-
tivity (approximately 0.3 V cm) for dc sputtering and (2)
only small (~3%) amount of O2 in the sputtering Ar+O2
gas is sufficient to produce transparent stoichiometric TiO2
films. In such sputtering system, arcing is automatically
avoided and reactive sputtering, even at p O2=0 Pa, is
carried out in the oxide mode. The absence of the
transition mode explains a good stability of reactive
sputtering process. Therefore, both the control of / O2 or
the control of p O2 can be used in formation of the
transparent stoichiometric TiO2 oxides (see Fig. 9). The
dependences p O2=f(/ O2) for both methods used to set a
selected p O2 value are practically identical. The films
sputtered at p O2=0 Pa are metal-rich and are opaque. When
a small amount of O2 is added, transparent films are
formed. However, the deposition rate a D decreases with
increasing p O2. In spite of this decrease in a D, transparent
oxide films can be sputtered with a high deposition rate
a D. In our labs, transparent TiOxc2 films were sputtered at
I d=4 A, U dc400 V, p O2=0.15 Pa, p T=1 Pa from the
sprayed TiO2x target of diameter 100 mm on glass
substrate located at d s-t=60 mm with the deposition rate
a Dc80 nm/min.
At present, there is a technical problem on how to spray
thick planar substoichiometric targets; spraying of thick
Fig. 9. The dependences p O2=f(/ O2) in reactive sputtering of TiOx films with unbalanced magnetron equipped with a TiO2x sprayed target of 100 mm in
diameter. DC sputtering at I d=4 A and p T=1 Pa.
cylindrical targets is possible. Besides, there is also an
open question if the stoichiometry of the sprayed target
changes during its lifetime when sputtered in Ar+O2
mixture.
7. Ion bombardment of growing films in pulsed sputtering
A pulsed sputtering process exhibits two important
properties: (1) time-dependent difference V pV fl, where
V p is the plasma potential and V fl is the floating potential of
the substrate, and (2) generation of ions of sputtered metal.
Both issues can be used for ion bombardment of the
growing film. This process very effectively densifies the
film during its growth and also can stimulate crystallization
of films sputtered at low deposition temperatures Ts. The
formation of films from ionized metal atoms is expected to
be a new advanced deposition process in the very near
future, which undoubtedly enables to produce new
advanced films with unique properties. At present, the
investigation of these properties is at its beginning and so
further the ion bombardment process is described only
briefly.
Any object immersed inside discharge is negatively
biased to the floating potential V fl with respect to the
plasma potential V p. Because V flb0, positive ions are
extracted from the plasma to the floating substrate and the
difference V pV fl determines the energy E i of the ion
acquired in a collisionless voltage sheath in front of the
substrate. Under the assumption of Maxwellian electron
energy distribution with an electron temperature Te and a
collisionless sheath, the energy E i of singly charged ions can
be expressed, using the formula for the difference V pV fl
[45] as follows,


Ei ¼ e Vp  Vfl ¼ ðkTe =2Þlnðmi =2:3me Þ ð4Þ
where k is the Boltzmann constant and e is the elementary
charge. The total energy E delivered to the growing film by
all bombarding ions is the product of energy E i and the total
 J. Musil et al. / Thin Solid Films 475 (2005) 208–218 215

Fig. 10. Time dependence of the electron density N e and the transverse electron temperature Te8 in hydrogen and helium microwave magnetoactive plasma
generated by power 2 kW CW at frequency 2.45 GHz and pressure 0.1 Pa. After Ref. [47].

flux of bombarding ions m i. It can be expressed either as an
energy delivered to the surface of the growing film
h i
E J=s cm2 ¼ Ei mi ¼ Ei Ne VB ¼ Ei Ne ðkTe =mi Þ1=2 / Te3=2 Ne ;
ð5Þ
or an energy delivered to the volume of the growing film
under the assumption of its constant density
h i h i
E J=cm3 ¼ Ei mi =aD ¼ E J=s cm2 =aD ½cm=s: ð6Þ
Here, N e is the electron density near the plasma–sheath
interface, V B is the Bohm velocity and a D is the deposition
rate of the film.
From Eq. (5), it is clearly seen that the energy delivered
to the growing film is proportional to the product Te3/2N e.
Just these two quantities, the electron temperature Te and the
electron density N e, strongly change in pulsed plasmas. At
the beginning of the pulse, when the plasma builds up and
its electron density N e is very low and increases from zero,
the electron temperature Te is on the contrary very high and
decreases with increasing time to a stationary value.
Although no measured data of Te and N e in a pulsed high-
power magnetron plasma were published till now [46], the
time development of Te(t) and N e(t) in the pulsed micro-
wave plasma is given in Fig. 10 [47] as an example. From
this figure, it is seen that Te at the pulse beginning achieves

Fig. 11. Energy distribution of Cu+ and Ar+ ions measured in front of the substrate (d st=100 mm) in a pulsed magnetron discharge operated with a Cu target at
a repetition frequency f r=1 kHz, length of voltage pulse 200 As, p Ar=1 Pa in (a) interval 50–70 As after the pulse beginning at average pulse current I da=5 A
(~25 W/cm2) and I da=50 A (~450 W/cm2) and (b) two time intervals 50–70 and 175–195 As (~650 W/cm2) after the pulse beginning and average pulse current
I da=50 A. After Ref. [49].
216 J. Musil et al. / Thin Solid Films 475 (2005) 208–218

high values up to approximately 1 keV. This value of Te
depends on energy delivered to the discharge. High
energetic ion bombardment with E iz100 eV at the begin-
ning of every pulse is followed by a low energetic ion
bombardment with E iV5 eV during a stationary state of the
pulse. A similar ion bombardment occurs in dc pulsed high-
power magnetron discharges and it makes possible to
produce dense films on unbiased substrates observed, for
instance, in Ref. [48]. In addition, it is worthwhile to note
that an efficiency of the ion bombardment during pulsed
magnetron sputtering will strongly depend on an operating
pressure p T=p Ar+p RG.
Very important feature of a pulsed magnetron discharge
is the production of ionized sputtered atoms Me+.
However, to produce Me+ ions, the magnetron must be
operated at high values of the target power loading, i.e. a
high power magnetron (HPM) must be used. This results
in intensive sputtering of the target and the rarefaction of
argon gas. The last effect is caused by argon gas heating
due to the energy transfer from the copper atoms leaving
the target with a kinetic energy of several eV. In this
process, the temperature T of Ar gas increases and this
increase in T is compensated by the decrease of Ar atoms
density n approximately according to the equation p=nkT,
where p is the pressure. Under these conditions, an
efficient ionization of Cu atoms in the bulk plasma takes
place due to its low ionization energy (7.72 eV) and Cu+
ions prevail over Ar+ ions in the plasma (see Fig. 11a and
b). Here, the effect of the target power density and Ar gas
rarefaction, respectively, is illustrated. This experiment
clearly shows that in HPM sputtering discharges the flux
of Me+ ions can be more than 10 times higher than that of
Ar+ ions and progressively increases with increasing time
from the pulse beginning. At I da=50 A (~450 W/cm2), the
number of ions in the plasma contains approximately 82%
and 96% Cu+ ions at the interval 50–70 As and at the end
of the pulses, respectively (see Fig. 11b). More detailed
analysis is given in Refs. [49, 50].
8. Reactive sputtering of hard nanocomposite films
The reactive magnetron sputtering can be used not only
for sputtering of nitrides, oxides and other compounds, for
instance, oxinitrides, but also for the production of nano-
composite films. Due to small (1–20 nm) grains, the
nanocomposite films exhibit new unique properties, which
exhibit enhanced properties, e.g. enhanced hardness,

Fig. 12. XRD patterns from Ti(Fe)Nx films as a function of partial pressure of nitrogen p N2. Deposition parameters: I d=3 A, U s=100 V, i s=1 mA/cm2,
Ts=3008C, d st=60 mm and p T=0.5 Pa. TiFe (90:10 at.%) target of 100 mm in diameter. After Ref. [53].
 J. Musil et al. / Thin Solid Films 475 (2005) 208–218
exceeding two or more times that of coarse-grained
materials [51,52]. Therefore now, the nanocomposite films
are intensively studied and new methods of their production
are developed.
A possibility to form nanocomposite films using a dc
reactive magnetron sputtering is demonstrated on a
deposition of Ti(Fe)Nx films with a low (V15 at.%) Fe
content [53] (see Fig. 12). Here, the development of
Ti(Fe)Nx films with a partial pressure of nitrogen p N2 and
intervals corresponding to individual sputtering modes are
displayed. From Fig. 12, it is clearly seen that inside the
transition mode of sputtering there is a transition region
(0.175 Pabp N2b0.212 Pa), in which the XRD patterns from
the Ti(Fe)Nx films exhibit at least two very low intensity
reflections. These films are (i) composed of a mixture of
very fine grains of different crystallographic orientations,
(ii) nearly stoichiometric x=N/(Ti+Fe)c1 and (iii) super-
hard with a microhardness Hz40 GPa. The rise of the
transition region is connected with a change of strongly
preferred y-TiN(200) orientation ( p N2=0.175 Pa) to
strongly preferred y-TiN(220) orientation ( p N2=0.212 Pa)
with increasing p N2. Such a jump change in preferred
orientation of grains in sputtered Ti(Fe)Nx films when p N2
is increased is a typical feature also for other sputtered
nitrides containing a small (V15 at.%) amount of the added
element (e.g. Y, Cu, Ni) forming a solid solution, see, for
instance, Zr–Y–N [54], Zr–Ni–N [55], Cr–Ni–N [56], Zr–
Cu–N and Zr–Ti–Cu–N [57]. These findings indicate that
the dc pulsed reactive magnetron sputtering could be a
very efficient method to produce nanocomposite films
based on nitrides. For more details on the formation of the
transition region in dc reactive magnetron sputtering, see
Ref. [53].
9. Trends of future development
The ratio a D oxide/a D Me achieved at present is high (up to
approximately 75%), but (i) the absolute value of a D oxide
should still be increased and (ii) the technological process
currently used for the production of the transparent
stoichiometric oxides should be simplified. This needs to
develop new sputtering systems, which will meet the
following requirements: (1) sputtering should be carried
out in deposition devices, in which the pumping speed S RG
of the pumping system for the RG is greater than a critical
value S c defined by Eq. (2), i.e. under the condition that
S RGNS c; (2) magnetrons should be operated with a full
target erosion and at high target loadings, which ensure that
the target surface will be free of oxides during sputtering; or
(3) sputtering should be carried out in an activated RG, i.e.
the stoichiometric oxides should be produced at lower
values of p RG compared to that used in the sputtering
systems where a neutral (molecular) RG is used. The
solution of these requirements is a huge challenge to
develop new advanced sputtering sources.
217
Acknowledgements
This work was supported in part by the Ministry of
Education of the Czech Republic under Projects No. MSM
235200002, ME 203 and ME 529.
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