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Surfaceand CoatingsTechnology 86-87 (1996)177-183

Comparison of the structure of PVD-thin films deposited with

different deposition energies
E. Lugscheider *, C. Barimani, C. Wolff, S. Guerreiro, G. Doepper
Materials ScienceInstitute, Aachen University of Technology, Templergraben 55, D-52056 Aachen, Germany

Abstract

Under the various available PVD processes, thin films can be deposited with higher or lower deposition energy, e.g., with or
without ion bombardment. Related to this deposition energy the structure and consequently the properties of the deposited films
can be directly influenced. The wide range of possible deposition parameters for the PVD-processes enables the use of materials
in form of thin films in a large scope of applications, as a result of the different properties which can be achieved. Particularly
high adhesion of thin films is always desired, which depends among other things on the microstructure of coatings.
The aim of this paper is to compare three different PVD deposition processes: cathodic arc evaporation, magnetron sputtering
and electron beam evaporation. These PVD processes are related to their film structure produced under three different conditions
and studied in terms of their deposition energies. Structure and morphology of the coatings are compared at identicaltemperatures
resulting in a model, which is suggested to explain how excitation of deposited films takes place. Besides condensation effects, the
momentum transfer of ions caused by biasing the substrates is obviously important and leads to film densification without
increasing the substrate temperature.

Keywords: PVD; Structure; Deposition energy; erN-coatings

1. Introduction determine the important parameters which may influence

Physical vapor deposition (PVD) processes are
increasingly used for the deposition of various coatings
on tools and components, e.g., to improve wear behavior
or corrosion resistance [1,2]. In addition to others,
Chromium nitride (CrN) is one of the popular and
universally used coating systems. The desired properties
of such coatings mainly depend on their microstructure,
which can be directly influenced by varying the level of
deposition energy during the deposition process.
Therefore, the presence of ion bombardment in addition
to heating up the substrates plays an important role in
thin films microstructure.
Depending on the type of PVD process and the target
materials, different degrees of ionization of the particles
and different quantities of ions in the vapor phase during
deposition have been reported [3-5]. However, several
structure zone models have been developed [6-11] to
* Corresponding author. Rheinisch-Westfaelische Technische
Hochschule Aachen, Lehr- und Forschungsgebiet Werkstoffwissen-
schaften, Augustinerbach 4-22, 52056, Germany. Tel.: 49 241 805329;
fax: 49 241 8888264.
the resulting microstructure of coatings, especially for
sputtering and electron beam evaporation. As a main
parameter the ratio (TITnJ between the deposition tem-
perature (T, in K) and the coating melting point (Tm ,
in K) has often been reported. Nevertheless, no compari-
son of the basic PVD processes has been carried out up
to now, considering the influence of ion bombardment.
In this paper the resulting microstructure of thin films
deposited by cathodic arc evaporation, sputtering and
electron beam evaporation are compared related to the
different predominating deposition energies, using erN
as a modern coating system.
2. Experimental details
Standard PVD processes, such as cathodic arc evapo-
ration, sputtering and electron beam evaporation, have
been used to deposit the coatings. Each of these depos-
ition methods represents a special state relating to
deposition energy, e.g., partial pressure, kinetic energy
and momentum transfer of vapor and gas atoms, cherni-

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PI! S0257-8972(96)03041-1
178 E. Lugscheider et al./Surfaceand Coatings Technology 86-87 (1996) 177-183
cal reactions, quantity and ionization degree of ionized
target atoms as well as intrinsic plasma motion. Table 1
gives an overview of typical parameters and the quantity
of ionized target atoms of some PVD processes [3].
The arc PVD-thin films were deposited in a Multi
Arc PVD 20" system equipped with a random arc source.
The coating plant is a commercially established system,
which is able to evaporate several metallic materials
with up to four targets. The CrN coatings had been
deposited in an reactive gas atmosphere (nitrogen). The
arc PVD-thin films were first carried out, because this
is the process showing highest energy caused by the high
quantity of ionized vapor particles, about 80% for Cr
[12], as well as the mean ionization degree of 2 [13],
using 0, 50, 100 and 200 V d.c. bias voltage. The resulting
temperatures were 250, 330, 400 and 500aC, measured
by a thermocouple at the backside of the 2-mm thin
samples. Prior to deposition the substrates had been
bombarded with chromium ions, which enhanced the
cleanness of the surface.
In the case of magnetron sputtering, only 5% of the
target material is ionized, whereas the rest is made up
of inert gas (argon) and reactive gas (nitrogen) ions.
Therefore the energy during deposition, especially for
reactive sputtering, must be lower than in arc evapora-
tion because the mean number of the participating ions
show lower atomic masses which leads to a decrease of
momentum transfer. The investigations were performed
in a Leybold Heraeus Z 400 Magnetron Sputter facility
(laboratory equipment). The substrates were coated
under reactive conditions using a commercially available
chromium target. The deposition mode was d.c., whereas
the biasing of the substrates was practiced under r.f.
conditions. To realize the same substrate temperatures
and deposition conditions, first the reachable temper-
atures, which could be achieved only by biasing the
substrates with the same voltage values as in the arc-
PVD experiments, were measured. Resulting temper-
atures were 115, 145, 175 and 21O aC, measured as
described above. The differences in temperature were
balanced by using a resistance heating system, which
enabled the same temperature values as reported for the
arc-PVD experiments. In the case of sputtering, the
Table 1
Typical parameters and quantity of target ions of different PVD processes [3]
Parameters Processes
Magnetron sputtering
Evaporation tool sputter effect
Phase transformation solid-vapor
Geometry of target/cathode any is possible
Quantity of ionized target atoms (%) 1-5
Additional ionization aimed
Inert gases necessary yes
Reactive deposition possible yes
substrates were cleaned by r.f-sputtering with argon
ions.
The electron beam evaporation was used as the depos-
ition process with the most obvious lowest deposition
energy. In this case the quantity of ionized vapor
particles is reported as less than 1% [13]. The depositions
were carried out in a modified CemeCon CCSOOE
electron beam evaporation laboratory apparatus. A
specific feature of this plant is a second electron beam
gun for heating up the substrates directly with electrons.
The substrates were only heated in this way up to the
temperature values as reported above, and no bias
voltage was applied. Therefore only a thermal excitement
of the condensing material took place. The evaporation
material was a commercially available Cr2N powder,
which was reactively evaporated by adding nitrogen
during deposition. Prior to coating, the surfaces of the
substrates were electron bombarded.
The substrate material was a typical HSS, namely S
6-5-2. The specimens were polished with a 6-llffidiamond
paste. In this context it should be noted that the melting
point of CrN is low enough (approximately 1740aC=
2013 K) to reach a zone 3 microstructure which is
reported in Ref. [6]. Considering the temperature when
the substrate S 6-5-2 starts loosing its hardness (560 aC=
833 K), with CrN as coating system, a ratio of
T/Tm =0.41 can be realized when only thermal excite-
ment takes place during condensation. This value marks
the beginning of the above-mentioned zone 3. However,
in the experiments we attempted to enable comparability
of the applied PVD processes, although the apparatus
geometry had a limiting effect. For example, the distance
between target and substrate was, in the case of sputter-
ing, only 40 mm, whereas for arc and electron beam
evaporation it was about 190 mm. This will be consid-
ered in Section 3. Table 2 gives an overview of the
various parameters.
3. Results and discussion
The investigation of the microstructure was carried
out by high resolution scanning electron microscopy.
Anodic arc ion plating Electron beam ion plating Cathodic arc ion plating
electron beam electron beam thermal arc
solid-vapor liquid-vapor solid-vapor
limited limited any is possible
5-40 <1 50-100
unusual aimed not necessary
no variable no
yes yes yes
 E. Lugscheider et al. / Surface and Coatings Technology 86-87 ( 1996) 177-183
Table 2
Processing parameters of the used PVD processes
Parameters
Quantity of ionized target atoms (%)
Target to substrate distance (mm)
Evaporation material
Inert gas
Reactive gas
Film thickness (J.ll11)
Resulting pressure during deposition (Pa)
The aim was to examine the dominant parameters which
are mainly responsible for the different microstructures
occurring, depending on the energy level of the con-
densing material; Fig. I and Fig. 2 show the observed
microstructures. Each figure compares the resulting
microstructures for electron beam (EB) evaporation,
sputtering and arc evaporation directly with respect to
the different deposition temperatures: 250, 330, 400 and
500°C. The SEM images are arranged in such a way as
to show the deposition energy increasing downwards.
On the SEM images it can be seen that, with increasing
temperature for each PVD process, the microstructure
of the thin films tends from a columnar form towards a
more "dense and uniform" structure. Moreover, the
surface of the coating becomes more and more smooth
with increasing substrate temperatures. This effect is
strongly developed for the arc-PVD coatings. At lower
temperatures, embedded droplets lead to defects in film
uniformity and preferential growth of crystallites, as can
be seen in Fig. 1(c). The arrow marks the pinhole where
a crystal was dislocated from its original growing place.
With increasing temperature and ion energy, this prefe-
rential growth is suppressed and the surface becomes
smoother. These observations were confirmed by SEM
images with a high magnification, on which the internal
microstructure of the thin films could be impressively
noticed. This is shown in Fig. 3 where the microstructure
of the electron beam and arc evaporated coatings con-
firm the supposition, while the substrate temperature
was 500°C for both.
Comparison of the different PVD processes for each
temperature level shows a densification of thin films
with increasing condensation energy. Whereas the
electron beam evaporated coatings have generally
columnar structures, the sputtered and arc evaporated
coatings show a more fibrous and "dense" microstruc-
ture. Obviously, the method of exciting the films during
deposition plays a more important role than substrate
temperature. In the SEM image in Fig. 3(a) it can also
be observed that the EB-PVD deposit shows a transition
from a columnar structure to recrystallization effects. In
addition to some columnar crystallites, crosswise growth
179
Processes
EB-PVD Sputtering Arc-PVD
<1 [13] 5 [3] 80 [12]
190 40 190
Cr 2N Cr Cr
Ar
N2 N2 N2
3.5 2.5 5
0.2 1.3 2
of grains across the columnar crystallite boundaries can
be observed simultaneously. Compared with this, the
microstructure of the arc-PVD thin films has no distinc-
tive grain boundaries, although both coatings were
deposited at the same temperature.
However, it can be seen that there are different ways
to realize an energetic excitement of PVD thin films
during deposition. The qualitative presentation of the
assumed excitement processes is suggested in Fig. 4. At
the same temperature, the resulting energies and the
deposition temperatures are shown for the different PVD
processes. The different values may be read either from
the resulting energy or the temperature scale, which is
indicated by the arrows. The basic bars up to 250°C
represent the influence on the temperature, whereas in
the case of sputtering and arc evaporation, the bars
above represent the effect on film densification. It has
been considered that the ratio of both bars results in an
approximated calculation (shown later in this paper).
Although in Fig. 4 the deposition temperature, for exam-
ple, is 250°C, the excitation processes are basically the
same for each temperature value.
In Fig. 4, it can be seen that, on one hand, there exists
a thermal excitement, which can be found on temper-
ature measurement. On the other hand, an energetic
supply of the condensing films can be ascertained by
investigating the resulting microstructure. The latter
observation is suggested because the coatings show a
"denser" microstructure caused by an increasein energy
levelof the condensing materials at the sametemperature
levels. As discussed above, the quantity of ionized
coating particles, and therefore their atomic masses, are
higher for arc evaporation, so that such deposited thin
films show very "dense" structures. This should be seen
in context to the lower energy PVD processes, sputtering
and electron beam evaporation, where coatings show a
more columnar structure.
Therefore the effect of ion bombardment on the
growing microstructure may be divided into two parts:
on one hand thermal excitement caused by condensation
effects, and on the other hand densification of coatings
caused by momentum transfer of energetic ions.
180 E. Lugscheider et al.fSurface and Coatings Technology 86-87 ( 1996) 177-183

(a)

(b)

(c)

Fig. 1. Resulting microstructures at deposition temperatures of 250 and 330°C for (a) electron beam evaporation, (b) sputtering, (c) arc evaporation.

Thornton named the densification effect "forward peen- estimated with the following formula, showing the
ing" [14], which leads to enhanced adatom migration atomic mass ratio (r) of the participating ions during
and bulk diffusion [15]. This is 0 bviously more effective deposition:
when a high quantity of ionized particles of the coating
material is available. The ratio between the atomic mass
quantity of target ions' atomic mass
of the target ions and other ions participating in conden-
sation, e.g., inert or reactive gases, appears to play an + quantity of gas ions'
r=-----------------
important role. This effect has been approximately atomic mass atomic mass of target material
 E. Lugscheider et al.jSurface and Coatings Technology 86-87 (1996) 177-183 181

(a)

(b)

(c)

Fig. 2. Resulting microstructures at deposition temperatures of 400 and 500°C for (a) electron beam evaporation, (b) sputtering, (c) arc evaporation.

1 Atomic masses: Cr=52, Ar=40, N 2=28. Conditions :

'ED-PVD= -=0.02 atom/ion ratio = 1; degree of ionization = 1 (single
52
charge).
0.05· 52+0.75 ' 40+0.20 ' 28 In the case of arc evaporation this ratio is 0.91,
'sputtering 0.73
52 because most of the participating ions are made up of
chromium. The sputtering ratio isjust 0.73 because most
0.8' 52+0.2' 28 of the ions are gas ions with less atomic mass, whereas
I'l\rc-PVD= =0,91
52 for electron beam evaporation the ratio is nearly zero,
182 E. Lugscheider et al.lSurface and Coatings Technology 86-87 ( 1996) 177-183
E [any unit]
(a)
(b)
Fig. 3. Internal microstructure at a deposition temperature of 500°C
for (a) electron beam evaporation, (b) arc evaporation.
since there is nearly no ionization. This is shown in
Fig. 4 by the bars representing the film densification.
The ratios of the different species were determined by
measuring the partial pressures.
Compared with the above-mentioned structure zone
models, no distinctive analogies are observed, particu-
larly in the case of sputtering and arc evaporation. One
reason may be that the substrate temperature range in
this investigation was to small. On the other hand, the
ion bombardment may cause another form of energetic
excitement of the reactive processes compared to only
heated substrates. Beyond that, the microstructures of
the sputtered films are nearer to the arc-PVD thin films,
than to the electron beam evaporated coatings. This
may also be explained by the above-suggested influence
of the atomic mass ratio between the participating ions.
A tendency from columnar crystallization towards a
microstructure like bulk material can be reported,
depending directly on the energetic excitement level of
the condensing film because of the increasing ada tom
mobility.
In addition to the above-discussed observations,
T [OCI
Deposition temperature 250°C
5
400
4 .- .-
.- '" 300
.- '"
3
II 200
2 i
~
, 100
I 0
EB-PVD Sputtering Arc-PVD
mom en tum transfer of ions (film den sifica tion)
therm al excitement by healing
thermal excitem ent by ion bombardment (condensation effects )
E ~ resulting ene rgy
Fig. 4. Schematic diagram of the influencing parameters for the ener-
getic excitement of PVD thin films during deposition.
differences in interface adhesion can be mentioned. The
EB-PVD coatings show lower adhesion to the substrates
than for arc evaporated layers. The best interface can
be observed for sputtered thin films (see Fig. I and
Fig. 2). Therefore, ion cleaning before deposition seems
to play an important role for interface bonding; r.f.-
sputter cleaning is the best way to achieve a good
adhesive interface zone.
4. Conclusions
A comparison of the microstructure of thin films
deposited by different PVD processes was carried out.
At the same temperature levels, ion bombardment was
added in the case of two PVD processes, to investigate
the effect of energetic excitement on the forming of thin
film microstructure. With increasing deposition temper-
ature on the one hand and increasing quantity of ionized
target atoms on the other, the microstructure tends from
a columnar form to a structure like bulk material. This
is accompanied by a smoothing of the surface coating.
As an attempt at an explanation, the effect of ionization
has been approximately estimated using a formula for
the ratio of participating ions. The resulting ratio values
were in good agreement with the SEM investigations,
 E. Lugscheider et al.jSurface and Coatings Technology 86-87 ( 1996) /77-183
because the ratios for sputter- and arc-PVD are similar
as are their resulting microstructures. In contrast to this,
the energy supply of the EB-PVD thin films is obviously
much lower than the determined ratio.
It can be seen that there is a direct dependence on
the method of exciting the deposited films. Two effects
are suggested when ion bombardment is used. On one
hand there is a thermal excitement caused by condensa-
tion effects, on the other hand the momentum transfer
of ions is responsible for a densification of coatings,
without resulting in an increase of deposition temper-
ature. In the present work, the different effects could
not be quantified. Further work needs to be carried out
on the effects taking place during deposition.
Acknowledgement
The authors would like to thank Dr. W. Rehbach
and N. Cammainadi, GfE-RWTH Aachen, for their
support and performance concerning the high resolution
scanning electron microscope images.
183
References
[I] J. Vetter and A.J. Perry, Surf. Coat. Technol., 61 (993) 305-309.
[2] O. Knotek, W.o. Munz and T. Leyendecker, 1. Vae. Sci. Technol.,
A 5(4) (1987) 2173.
[3] C. StoBel, Doctorial thesis, Aachen University ofTechnology, 1991.
[4] A. Plyutto, A.V.N. Ryzhkov and A.T. Kapin, Sou. Phys. JETP,
20(2) (1965) 328-337.
[5] W.D. Davies and RC. Miller, 1. Appl. Phys., 40 (5) (1969)
2212-2221.
[6] B.A. Movchan and A.V. Demshichin, Phys. Metals Metallogr.,
28(4) (1969) 83-90.
[7] J.A. Thornton, 1. Vac. Sci. Technol., A 4 (6) {Nov.j'Dec. 1986).
[8] R. Messier, A.P. Giri and R.A. Roy, 1. Vue. Sci. Technol., A 2 (2)
(1984) 500-503.
[9] J.V. Sanders, in J.R. Anderson (ed.), Chemisorption on Metallic
Films 1, London and New York, 1971, pp. 1-38.
[10] M. Lardon, R. Buhl, H. Signer, H.K. Pulker and E. Moll, J. Vae.
Sci. Technol., A 2(2) (1984) 500-503.
[11] C.R.M. Grovenor, H.T.G. Hentzell and D.A. Smith, Acta
Metall.,32 (1984).
[12] H.J. Scholl, Doctoral thesis, Aachen University of Technology,
Verlag Mainz, Aachen, 1993.
[13] R.F. Bunshah (ed.), Deposition Technologies for Films and Coat-
ings, Noyes Publications, Park Ridge, NJ, USA, 1982.
[14] J.A. Thornton, Thin Solid Films, 171 (1989) 5-31.
[15] T. Tagaki, 1. Vae. Sci. Technol., A 2(2) (1984) 382-388.