Thin Solid Films 339 (1999) 203±208

Phase transition and properties of Ti±Al±N thin ®lms prepared by

r.f.-plasma assisted magnetron sputtering
Min Zhou a,*, Y. Makino a, M. Nose b, K. Nogi b
a
Joining and Welding Research Institute, Osaka University, 11-1 Mihogaoka, Ibaraki, Osaka 567-0047, Japan
b
Takaoka National College, Futagami 180, Takaoka City, Toyama 933, Japan
Received 11 June 1998; accepted 21 August 1998

Abstract
Pseudobinary (Ti12xAlx)N ®lms were synthesized by a new inductively combined rf-plasma assisted planar magnetron sputtering method.
From X-ray diffraction measurement, the deposited (Ti12xAlx)N ®lms were identi®ed as having the B1 structure up to 50 mol% Al (x ˆ 0:5).
In the range from x ˆ 0:6 to x ˆ 0:7, two phases with the B1 and B4 structures were observed. These results suggest that the critical
composition for the phase change from B1 to B4 structure is located between 50 mol% Al and 60 mol% Al. The critical composition decided
experimentally shows a discrepancy with the theoretically predicted value (65 mol% Al), which may arise from a somewhat high substrate
temperature (4508C) in this study. Oxidation resistance increases with increasing the Al content in the (Ti12xAlx)N ®lms up to 70 mol% Al,
irrespective of coexistence of the B1 and B4 phases in the (Ti12xAlx)N ®lms with x ˆ 0:6 and x ˆ 0:7, while both the hardness and Young's
modulus show a maximum value, respectively. Thus, it is indicated that the existence of the (Ti12xAlx)N ®lms with the B1 structure is quite
effective for improving the oxidation resistance, and the appearance of the B4 phase in the pseudobinary nitride ®lms degrades mechanical
properties such as the hardness and Young's modulus. q 1999 Elsevier Science S.A. All rights reserved.
Keywords: (Ti12xAlx)N ®lms; Phase transitions; Sputtering; Hardness

1. Introduction
Hard material coatings are of continuously increasing
interest for wear reduction of working tools. TiN, TiC and
diamond-like carbon (DLC) ®lms are the most widely used
coatings for this purpose [1,2], especially TiN because of its
excellent properties and gold color [3,4]. However, there are
still several drawbacks such as hardness, adhesion, friction
and oxidation resistance properties that limit the practical
application of TiN. In order to improve these properties,
ternary and multilayer coatings such as (Ti,Al)N, (Ti,Zr)N
and (Ti,Nb)N [1,2,5,6] have been investigated. Among
these, the addition of aluminum in TiN to form (Ti,Al)N
ternary solid solution is attractive due to the signi®cant
enhancement of anti-oxidation and mechanical properties
in comparison with TiN [3,6,7].
In the equilibrium Ti±Al±N ternary phase diagram, Ti, Al
and N appear to have essentially no solubility in AlN, TiN
and TiAl, respectively [8]. Up to now, there have been some
reports about (Ti,Al)N thin ®lms, but most of them concen-
trate on the properties. Few reports about the phase transi-
* Corresponding author. Tel.: 1 81-6-8798663; fax: 1 81-6-8798653;
e-mail: zhoum@jwri.osaka-u.ac.jp.
0040-6090/99/$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.
PII: S 0040-609 0(98)01364-9
tion and the relationship between the phase transition and
properties are found.
In this study, pseudobinary (Ti12xAlx)N ®lms were
synthesized on stainless steel 304, quartz glass and glass
ceramic substrates by a new inductively combined r.f.-
plasma assisted planar magnetron sputtering method from
pure titanium and aluminum targets in a mixture of Ar and
N2. The phase transition and the relationship between the
phase transition and properties were studied in detail.
2. Experiment
2.1. Film preparation
Fig. 1 shows the r.f.-plasma assisted planar magnetron
sputtering apparatus used in the present study (MPS-200-
HC3, ULVAC Co., Japan). In this system, both Al and Ti
are simultaneously deposited on the substrate using two
targets. An r.f. generator, operating at 13.56 MHz, powers
the two targets and two helix coils just above the two
targets. Using the helix coil, an additional inductively
coupled r.f. discharge is generated just in front of the
magnetron target. This additional r.f. discharge not only
204 M. Zhou et al. / Thin Solid Films 339 (1999) 203±208

angle mode (Seeman±Bohlin, SB, mode) and u ±2u mode

(Bragg±Brentano mode). The grazing angle mode
(Seeman±Bohlin mode) was used to study the phase and
crystal structure of the thin ®lm and the u ±2u mode
(Bragg±Brentano mode) was used to study the orientation
of the thin ®lm. In the present study, 48 was used as the
incident beam angle in the SB mode.
The atomic ratio of titanium to aluminum in the as-depos-
ited ®lms was determined by electron probe microanalysis
measurement (JXA-8600, JEOL, Japan) with the WDX
method. Pure TiN and AlN were used as the reference mate-
rials and the ZAF correction method was applied.

2.3. Mechanical properties

The hardness and Young's modulus of the (Ti12xAlx)N

®lms were measured by an ultra micro-indentation system
(UMIS-2000, CSIRO, Australia) which used the Swain
method [10,11]. The indenter was a Berkovich diamond
Fig. 1. Schematic diagram of the deposition apparatus. pyramid indenter. A load of 5 mN was employed so that
the penetration depth of the indenter was less than 10% of
strongly increases the plasma density but also enables the the ®lm thickness. For each indentation, the indentation load
targets to be sputtered at very low pressures. The ionization was incrementally increased in 40 steps and the penetration
is also strongly increased, even up to 10 times compared depth was measured at each step. The hardness data and
with normal planar magnetron sputtering [9]. The detailed Young's modulus data were determined from the mean
experimental conditions are given in Table 1. The composi- value of several measurements.
tions of the pseudobinary ®lms were controlled by changing
the ratio of r.f.-power supplied to the Al cathode to that
2.4. Residual stress
supplied to the Ti cathode. The ®lms were deposited on
stainless steel 304, quartz glass T4040 and glass ceramic The evaluation of the ®lm stress was carried out with
PEG3130C substrates. Before sputtering, the stainless surface pro®le and roughness measurement machine
steel substrates were polished to an average roughness of (Form Talysurf Series S4, Rank Taylor Hobson Ltd., UK).
about 10 nm. Cleaning was performed with acetone and The change of curvature induced in the sample because of
propanol in an ultrasonic bath. the stress in the deposited ®lm was investigated by this
machine. A clean, undeposited blank glass ceramic
2.2. Film analysis
substrate was ®rst measured prior to ®lm deposition. The
The phase and crystal structure of as-deposited ®lms were data were then compared with those taken after the ®lm
identi®ed by X-ray diffractometry using Cu Ka radiation deposition. The point-by-point subtraction data were ®tted
with a thin ®lm goniometer (M03X, Mac Science Co., with a straight line where the slope was inversely propor-
Japan). Scans were made in different modes, namely grazing tional to the radius of the sample. The ®lm stress s was
calculated using the following equation that was derived
Table 1 from the Stoney equation [12]:
Experimental conditions
ET 2
Apparatus sˆ 4d …1†
Target purity (%) Ti 99.99 3…1 2 n†L2 t
Al 99.99
Target size (mm) 51 where E is Young's modulus of the substrate, n is Poisson's
R.f. power of cathode (W) Ti 150, Al 0±150 ratio of the substrate, T is the thickness of the substrate, L is
R.f. power of coil (W) Ti 50, Al 50 the length of the substrate, t is the thickness of the ®lm
Gas purity (%) Ar 99.9999 (t p T) and d is the deformation in the center of the
N2 99.9999
Gas ¯ow (m 3/s) Ar 1:67 £ 1026
substrate after deposition.
N2 8:33 £ 1027
Sputtering pressure (Pa) 0.3
2.5. Electric resistivity of the ®lms
Substrate temperature (8C) 450
TargetÐsubstrate distance (mm) 180
Film thickness (mm) 0.4Ð1
The electric resistivity was measured by the four-probe
method [13] at room temperature.
 M. Zhou et al. / Thin Solid Films 339 (1999) 203±208
Fig. 2. XRD patterns of the as-deposited (Ti12xAlx)N ®lms.
2.6. Oxidation of the ®lms
The weight gain due to the oxidation of the ®lms was
measured using the thermo-gravity method (TGA-50,
Shimadzu, Japan). A quartz glass substrate was used in
Fig. 3. Crystal structure of phases in the (Ti12xAlx)N ®lms.
205
order to prevent reaction between the ®lm material and
the substrate and also to prevent substrate oxidation. The
samples were heated in air. The temperature was increased
at a rate of 5 K/min.
3. Results and discussion
3.1. Structure and phase transition of the (Ti12xAlx)N ®lms
Fig. 2 shows the X-ray diffraction patterns obtained from
the as-deposited (Ti12xAlx)N ®lms (x ranging from 0 to 0.8).
When the Al concentration (x) was changed from 0 to 0.6,
the ®lms were identi®ed as having the cubic B1 structure
which is the same structure as pure TiN. When x varies from
0.6 to 0.7, two phases with the cubic B1 structure and the
hexagonal B4 structure were detected. For x exceeding 0.7,
only a single phase with the hexagonal B4 structure was
observed. A summary of the phase relations in the ternary
(Ti12xAlx)N system is shown in Fig. 3. The atomic ratio of
the as-deposited ®lms was determined by EPMA with the
WDX method, combined with the ZAF correction method
using pure TiN and AlN as the reference materials. The
lattice parameter of the B1 structure, as a function of x in
the (Ti12xAlx)N thin ®lms, is shown in Fig. 4. With increas-
ing x, the lattice parameter in the B1 structure decreases
linearly from 4.2448 A Ê for TiN to 4.1462 A Ê for
(Ti0.3Al0.7)N. This suggests that titanium atoms in the TiN
lattice are substituted by aluminum atoms with smaller
atomic radius, although both titanium and nitrogen atoms
in the TiN have a coordination number of 6, while in AlN
the coordination numbers of aluminum and nitrogen atoms
are 4 [14].
The critical composition decided experimentally shows a
discrepancy with the theoretically predicted value made by
one of the authors of this paper [15,16]. In these papers, the
critical composition for B1/B4 was predicted by the two
band parameters, hybrid function H and gap reduction para-
meter S, and the crystal structure map based on these para-
meters and the composition factor finv. According to these
calculations, the critical composition for the B1(TiN)/
B4(AlN) phase transition in the Ti±Al±N system was
about 65 mol%. This suggested that the B1 phase would
transform to the B4 phase directly when the AlN content
was 65 mol% in the Ti±Al±N system.
As shown in Fig. 2 and Fig. 3, the coexistence region of
the B1 and B4 phases was observed in the composition
range from 60 mol% Al to 70 mol% Al. The coexistence
is probably attributed to high substrate temperature at
deposition because non-equilibrium B1 phase close to the
critical composition becomes unstable with increasing
substrate temperature.
3.2. Hardness and Young's modulus of the (Ti12xAlx)N ®lms
The results of Young's modulus and microhardness
measurements with a 5 mN load on the as-deposited
206 M. Zhou et al. / Thin Solid Films 339 (1999) 203±208
Fig. 4. The lattice parameters as a function of the Al concentration in the
(Ti12xAlx)N ®lms.
(Ti12xAlx )N ®lms are shown in Fig. 5. It shows that the
hardness and Young's modulus increase with increasing
Al concentration and have a maximum value at an Al
concentration of 50 mol%. These hardness values are
much higher than those of pure TiN ®lm. After the Al
concentration exceeds 50 mol%, the hardness and Young's
modulus decrease rapidly. The rapid decrease is consistent
with the appearance of the B4 phase.
Up to now, the reason why the substitution of Al atoms
for Ti atoms in the non-equilibrium (Ti12xAlx)N ®lm with
B1 structure can increase the hardness has still not been
clearly explained. However, a simple explanation can be
found on the basis of bonding characteristics. According
Fig. 5. The hardness and Young's modulus as a function of the Al concen-
tration in the (Ti12xAlx)N ®lms.
Fig. 6. The residual stress as a function of the Al concentration in the
(Ti12xAlx)N ®lms.
to Cohen [17], the bulk modulus increases with decreasing
nearest neighbor distance in AB compounds with tetrahe-
dral coordination. Assuming that the increase of bulk modu-
lus corresponds to the increase of hardness, the increase of
hardness of the compound can be explained by the decrease
of interatomic distance in the compound. As shown in Fig.
4, the interatomic distance of (Ti12xAlx)N ®lms decreases
with increasing Al content in the B1 lattice, so the increase
of hardness in these ®lms originates from the decrease of
their interatomic distance. Further, because the relation
between interatomic distance (d) and covalent band gap
(Eh) is given by the formula Eh ˆ kd 22:5 [18], the origin
of the hardness increase is probably connected with the
increase of covalent energy in these non-equilibrium
(Ti12xAlx)N ®lms
3.3. Residual stress of the (Ti12xAlx)N ®lms
Fig. 6 shows the results of the residual stress calculation
of the ®lms. It indicates that the residual stress in the
(Ti12xAlx )N ®lms is compressive, but there are two sharp
sudden changes at Al concentrations of 20 mol% and
60 mol%, respectively. The reasons for these two sudden
changes in the residual stress are different.
When the Al concentration increases from 0 mol% to
20 mol%, the compressive residual stress increases sharply
because the Al atoms bomb into the TiN lattice and generate
a very obvious atomic pinning effect.
When the Al concentration increases from 50 mol% to
60 mol%, the compressive residual stress decreases sharply
because the phase transition from the B1 to B4 structure
occurs. The AlN lattice parameter is smaller than the TiN
lattice parameter, so the volume shrinks when the B1 phase
 M. Zhou et al. / Thin Solid Films 339 (1999) 203±208
Fig. 7. The electric resistivity as a function of the Al concentration in the
(Ti12xAlx)N ®lms.
transforms to the B4 phase. The shrinking of the volume
generates tensile stress, so the compressive residual stress of
the ®lms decreases sharply.
3.4. Electric resistivity of the (Ti12xAlx)N ®lms
TiN conducts electricity similar to the metal, but AlN is a
very good insulator. The electric resistivity of (Ti12xAlx)N
®lms deposited on the silica glass substrates was measured
at room temperature. The results are shown in Fig. 7. The
Fig. 8. Oxidation curves as a function of the Al concentration in the
(Ti12xAlx)N ®lms.
207
electric resistivity of (Ti12xAlx)N ®lms in the B1 structure
increases linearly. However, when the Al concentration
exceeds 50 mol%, the phase transition from B1 to B4
occurs. Because AlN is a very good insulator, the electric
resistivity of the (Ti12xAlx)N ®lms increases sharply from
23.5 V cm for (Ti0.5Al0.5)N to 136 V cm for (Ti0.4Al0.6)N.
3.5. Anti-oxidation property of the (Ti12xAlx)N ®lms
One of the most signi®cant disadvantages of TiN thin ®lm
is that the oxidation of TiN is initiated at as low as 5508C,
which is considerably lower than the typical working
temperature for high speed cutting tools (up to 7008C) [2].
But (Ti12xAlx)N ®lms have much higher thermal stability
than TiN ®lms[6,7]. Fig. 8 shows the oxidation curves of
(Ti12xAlx)N ®lms compared with a TiN ®lm measured by
the TG method. The initiation of oxidation of pure TiN ®lm
occurred at 5508C in air, while the (Ti12xAlx)N ®lms with a
cubic B1 structure began to oxidize at higher temperature
than 5508C. These temperatures for the initiation of oxida-
tion become higher with increasing x value and the
(Ti12xAlx)N ®lms with x ˆ 0:6 and x ˆ 0:7 show high stabi-
lity for oxidation in air up to 9508C, irrespective of the
coexistence of the B4 phase. Thus, it is expected that the
B1-type metastable (Ti12xAlx)N ®lms, especially with
higher AlN content, show quite high stability for oxidation.
The reason for the high oxidation resistance of the B1-type
metastable (Ti12xAlx)N ®lms remains unclear, although it
has been suggested by theoretical calculation and XPS
measurement that the oxidation of titanium in these meta-
stable (Ti12xAlx)N ®lms is suppressed because the electric
energy of titanium is stabilized in the B1-type lattice [19].
4. Summary
Using a new inductively combined r.f.-plasma assisted
planar magnetron sputtering method, pseudobinary
(Ti12xAlx)N ®lms were synthesized on stainless steel 304,
quartz glass and glass ceramic substrates. Pure titanium and
aluminum targets were used to deposit the ®lm simulta-
neously.
Up to 50 mol% Al, the formation of (Ti12xAlx)N ®lms
with the B1 structure was identi®ed by XRD, and the coex-
istence of the B1 and B4 phases was observed in the range of
aluminum content from 60 mol% to 70 mol%. The experi-
mentally decided critical composition (around 55 mol% Al)
for the phase transition from B1 to B4 was found at a lower
Al content than the theoretically predicted value (about
65 mol% Al). The discrepancy is attributed to the somewhat
higher substrate temperature.
Irrespective of coexistence of the B1 and B4 phases, the
synthesized pseudobinary (Ti12xAlx)N ®lms containing
60 mol% Al and 70 mol% Al showed quite excellent resis-
tance to oxidation in air, resulting in proof of the excellence
of the metastable (Ti12xAlx)N ®lms with the B1 structure for
anti-oxidation. Improvement of the hardness and Young's
208 M. Zhou et al. / Thin Solid Films 339 (1999) 203±208
modulus were also observed for these pseudobinary nitride
®lms, but it is suggested that the coexistence of the B1 and
B4 phases is not suitable for mechanical properties such as
hardness and Young's modulus.
Acknowledgements
The authors would like to thank Mr Nakatsuka for his
help in EPMA.
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