Journal of Scientific &VINH & NGOC

Industrial : DEPOSITION OF TiAlSiN HARD FILM BY CATHODIC ARC PLASMA

Research 273
Vol. 70, April 2011, pp. 273-277

Deposition of TiAlSiN hard film by cathodic arc plasma evaporation using

a single target combined with a shield filter
Pham Van Vinh1* and Tran Vu Diem Ngoc2
1
Hanoi National University of Education, 136 Xuan Thuy Road, Cau Giay District, Hanoi, Vietnam
2
Hanoi University of Technology, 1 Dai Co Viet Road, Hanoi, Vietnam

Received 16 December 2010; revised 28 February 2011; accepted 03 March 2011

Films of TiAlSiN were deposited on AISI H13 tool steel substrate by a cathodic arc-plasma deposition system using a single
TiAlSi alloy as target. Presence of TiN crystal phase was found on films, but no XRD peaks related to Al and Si were found.
Hardness, morphology and adhesion of films changed with different deposition parameters. Maximum hardness (36.29 GPa) of
films was found on sample deposited at 300°C with 3x10 3 Torr and cathode arc current of 45 A.

Keywords: Cathodic arc plasma, Hardness, Scratch, Shield filter, Single TiAlSi alloy target, TiAlSiN, Wear

Introduction TiAlSiN films deposited by cathodic-arc evaporation using

TiN is known as a hard coating material but it gives
limited oxidation resistance at high temperatures during
cutting process1. In comparison with TiN, TiAlN coatings
have better oxidation resistance and remain stable at
higher temperature. Ti 0.5 Al 0.5 N has an oxidation
temperature of 700°C, whereas TiN begins to oxidize at
500°C2. Shizhi et al3 successfully deposited superhard
TiSiN films, thus adding silicon into TiAlN films to
improve mechanical properties. In general, dislocation
with some mobility, microcracks and other structural
defects of grain boundaries, formed during deposition,
results in decrease of strength and hardness of materials.
Materials, in which nanocrystalline TiAlN embedded into
amorphous Si3N4 matrix, can prevent dislocation within
nanocrystals from sliding through amorphous grain
boundary matrix even under highly applied stress1,4,5.
When silicon is added to films by using a multitarget
approach with at least one target being a silicon-alloy,
TiAlSiN films deposited exhibit very good mechanical
properties6-10. TiAlSiN films deposited by hybrid system
also gave good results 11 . However, depositing of
composite films has required a complicated configuration
system with many targets1,5-15. Münz et al16 showed that
number and size of droplets would increase if melting
point of targets was low. Mechanical properties of
*Author for correspondence
Tel: +84-437548442
E-mail: vinhpv@hnue.edu.vn
dual targets have been studied17,18.
In this work, to retain simplicity of a single target
while minimizing formation and affect of droplets, a shield
filter was introduced, resulting in a simplified process
with enhanced mechanical properties. Also, properties
of TiAlSiN composite films deposited by cathodic arc
evaporation using a single TiAlSi alloy target were
studied.
Experimental Section
TiAlSiN films were deposited on AISI H13 tool steel
substrate by typical cathodic arc-plasma deposition
equipment (Fig. 1). A single target (diam, 63 mm) made
of Ti65Al30Si5 alloy (Ti, 65; Al, 30; and Si, 5 wt %) is
installed on chamber wall. Substrates were placed in
front of target (distance, 280 mm). Small metal sheet
between target and substrate acts as shield filter to reduce
droplets on films. Substrates were manually ground with
SiC papers, polished with Al2O3 powder using a low-
speed polishing machine, cleaned ultrasonically in pure
alcohol and etched in argon gas with a current (0.6 A)
for 10 min. Crystalline phases were determined by an
X-ray diffractometer (Rigaku, RAD-3C). Compositional
analysis was carried out by electron probe micro-
analyzer (EPMA). Morphology was observed using a
scanning electron microscope (SEM) and optical
microscope. Mechanical properties were studied using
Vickers hardness, a wear tester and a scratch tester.
274 J SCI IND RES VOL 70 APRIL 2011

12 0

111
10 0

80

200
Intensity (a.u)

220
60

311
40

20

0
20 30 40 50 60 70 80
2 q ( D e g re e )
Fig. 2—XRD diffractogram of TiAlSiN films

Fig. 1—Schematic diagram of experimental apparatus

Results and Discussion

TiAlSiN films deposited (pressure, 3.0 x 10-3 Torr;
temp., 300°C; and bias voltage, -150V) were used for
microanalysis. XRD pattern (Fig. 2) shows presence of
TiN crystalline peaks. Although compositional analysis
a)
shows contents of Al (12.715%) and Si (2.897%), no
peaks related with Al and Si were found, indicating that
nitrides of Al and Si in films were amorphous. Two types
of clusters corresponding to crystalline and amorphous
phases are clearly visible in FE-SEM cross sectional
image (Fig. 3a). It is therefore possible for crystalline
grains to be grown as a columnar grain mixed with
amorphous clusters. These results confirmed that TiAlSiN
films are a composite of crystalline TiN and amorphous
aluminum and silicon nitride. Looking into FE-SEM image
of surface of films (Fig. 3b), droplets and clusters make b)
surface rough, thereby adversely affecting mechanical
properties of films. In arc-cathodic method, microparticles
(size, 0.1-100 µm) transferred from target to substrate15
may cause this problem. It is possible to improve surface
morphology by using a filter19,20. Surface morphology of
films deposited with shield filter shows significant droplet
reduction (Fig. 3c).
Deposition temperature influences strongly the
reaction constant, diffusion of defects, surface free energy
etc. By increasing substrate temperature, mobility of
atoms is also increased, leading to a structure with less c)
imperfection. Films deposited at 300°C exhibited Fig. 3—FE-SEM micrograph of: a) cross section of film deposited
(bias voltage, -150 V); b) surface morphology of film deposited
maximum hardness (Fig. 4a). Also, film surface showed without filter; and c) surface morphology of film deposited with a
smooth morphology. Keeping temperature (300°C) and shield filter
 VINH & NGOC : DEPOSITION OF TiAlSiN HARD FILM BY CATHODIC ARC PLASMA 275

36
a)
34
b)
32

30 c)
Hardness, GPa

28
d)
26
e)
24

22
Fig. 5—Optical micrographs of scratch tracks of films deposited
with various nitrogen pressure: a) 0.5×10-3 Torr; b) 2.0×10-3 Torr;
20 c) 3.0×10-3 Torr; d)5.0×10-3 Torr; and e) 7.0×10-3 Torr

18 36
180 200 220 240 260 280 300 320 340 360

Temperature, °C 34

36
32

34 Hardness, GPa 30

32
28
Hardness, GPa

30
26

28
24

26
24
22
0 1 2 3 4 5 6 7
Pressure, 10-3 Torr
Fig. 4—Hardness of films deposited with: a) different
temperatures; and b) different nitrogen pressure
bias voltage (-150 V) constant, pressure was varied
(0.5x10-3 - 7 x10-3Torr) for each sample (Fig. 4b) and
observed that hardness increases with increase of
pressure. However, further increasing pressure
decreased hardness. Optical micrographs of these films
(Fig. 5) show that width of scratch tracks increase as a
function of pressure. Broken track dentations, found on
samples deposited at higher pressure, result from bad
adhesion. At low pressure during reactive deposition, low
nitride concentrations result in increasing defects in films
that reduces hardness. Samples deposited at pressure
below 3 x 10-3 Torr (optimal pressure) showed low
hardness. Above this pressure, hardness starts to fall
22
0 50 100 150 200
Bias voltage, -V
Fig.6—Hardness of films deposited with different bias voltage
8
again. Increase in nitrogen pressure leads to an increased
nitride density that decreases kinetic energy of particles
so inhibiting transfer to substrate. Low kinetic energy
particles will adhere weakly to substrate leading to bad
films. This was confirmed by an optical microscope that
revealed some cracks on samples. Cracked films gave
rise to cracked dentations track and decreased hardness.
Hardness of films deposited at 300°C and 3.0 x 10-3 Torr
as a function of bias voltage (Fig. 6) increases from 23.54
GPa to 34.32 GPa with increasing bias voltages from
0 V to -150 V; beyond this, hardness decreases. Under
a bias voltage, ions of nitride and particles are driven to
substrate. Ions’ bombardment of sample surface removes
weakly adhering particles and transfers energy to
substrate where film grows. Therefore, films deposited
with a bias voltage show better adhesion and hardness
than those without bias voltage. Hardness decreased
beyond –150 V. Here ionic bombardment resulting from
276 J SCI IND RES VOL 70 APRIL 2011
a)
b)
c)
d)
e)
Fig. 7—Optical micrographs of scratch tracks of films deposited
with various bias voltages: a) No bias; b) -50V; c)-100 V; d) -150
V; and e) -200 V
a)
b)
c)
Fig. 9—Optical micrographs of wear tracks of films deposited
with various arc current: a) 25 A; b) 35 A; c) 45 A
high bias voltage impinges on substrate resulting in
damage to films and a decrease in hardness.
Scratch tracts change with increasing bias voltage
(Fig. 7). Scratch track of films deposited without bias
voltage is rougher than with a bias voltage. Films deposited
without bias also have rough surface and bad adhesion.
Hardness increased with an increase of arc current
(Fig. 8). Hardness reached 36.29 GPa in films deposited
with arc current of 45 A. Increase of arc current
increases not only deposition rate but also energy of
particles. Films deposited with high arc current had high
particle energy leading to improved transfer to substrate
giving more hardness. Wear tracks of films (Fig. 9) show
broadened wear track width on the sample deposited at
arc current of 35 A and narrowed track on the sample
deposited at an arc current of 45 A, indicating that sample
deposited with arc current of 45 A exhibits a good wear
resistance.
Comparing with reported 17 hardness gained,
hardness gained in present work is a little lower. However,
with simple technique, these results are acceptable.
36
34
Hardness (GPa)
Hardness, GPa
32
30
28
25 30 35 40 45
Current, A
Fig. 8—Hardness of films deposited with different arc current: a)
25 A; b) 35 A; and c) 45 A
Conclusions
TiAlSiN composite films with mixed crystalline and
amorphous phases were deposited successfully on AISI
H13 tool steel by using an arc cathodic technique with a
single TiAlSi alloy target. Droplets and consequential film
degradation were significantly reduced when a shield
filter was used in deposition process. Optimum hardness,
best adhesion and wear resistance were found on samples
deposited at: temp., 300°C, pressure, 3x10-3Torr; bias
voltages, -150V; and arc current, 45A.
Acknowledgments
This work was supported by Grant No. 103.03.93.09
from NAFOSTED. Authors thank Prof Sun Kyu Kim
for contribution to this paper.
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