NOLW/

ELSEVIER Surface and Coatings Technology81 (1996) 164-171

41#/7N6,,

Stress and oxidation behaviours of r.f.-sputtered (Ti,A1)N films

Chi-Tung Huang, Jenq-Gong Duh *
Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan Received 10 October 1994

Abstract
(Ti,A1)N thin films were deposited onto A2 steel by reactive r.f. magnetron sputtering. The residual stress of as-deposited films was compressive for TiN and switched to be tensile for Ti0.61Alo.39N. After heating at 600 C, the TiN film spalled off and iron oxides formed on the substrate surface, while there existed an unoxidized (Ti,A1)N layer adjacent to the substrate in the oxidized (Ti,A1)N films. The near surface of the (Ti,A1)N coating was a mixture of TiO 2 and amorphous A120 3 and the diffusion of iron from the substrate through the grain boundary or pinholes resulted in the formation of iron oxides. The (Ti,A1)N films with higher A1 contents after oxidation maintained a red-blue colour. The addition of A1 atoms promoted the oxidation resistance of the (Ti,A1)N coating in comparison with pure TiN. As the A1 contents were increased, the anti-oxidation of the (Ti,A1)N films was enhanced, while the scale thickness and the diffusion of iron through the coating were significantly decreased. Keywords: Magnetron sputtering; Residual stress; Oxidation

1. Introduction
Titanium nitride (TIN) with the characteristics of hardness and gold-yellow colour can be applied as a hard coating to improve the lifetime of a tool surface [ 1-4]. However, there also exist several drawbacks that limit the practical application of TiN. In particular, the oxidation of TiN coating can be initiated at as low as 550 C [5], and this would restrict the lifetime of the tool steel. In recent years there has been an increasing interest in developing films of ternary compounds to improve further the properties of binary coatings. The investigations have been directed at TiN-based compounds [6,7] such as (Ti,A1)N, (Ti,Zr)N and (Ti,Nb)N. Among these compounds, the addition of aluminium in TiN to form (Ti,A1)N ternary solid solution becomes an attractive subject due to the enhancement of antioxidation and mechanical properties in comparison with TiN [8]. Aluminium nitride (A1N) coatings are proved to have excellent mechanical, anti-corrosion, and antioxidation properties [9,10]. The deposition of (Ti,A1)N films with various compositions onto A2 tool steel was recently achieved in our group by reactive r.f. magnetron sputtering [11]. With the addition of aluminium in the TiN cell, the structure of the (Ti,A1)N was identified to be an f.c.c. * Corresponding author. 0257-8972/96/$15.00 1996 ElsevierScience S.A. All rights reserved SSDI 0257-8972 ( 95 ) 02479-4

B1 structure and the surface hardness of the A2 tool steel was improved significantly in comparison with pure TiN film. The purpose of this study is to investigate further the stress and oxidation behaviour of the (Ti,A1)N-coated A2 tool steel. In this research, the stress of the as-deposited films was measured and the oxidation behaviours of the (Ti,A1)N films were studied through thermal cycles. The phase and crystal structure of the films after oxidation were identified with an X-ray diffractometer by the grazing-incidence technique and the surface topography of the films were analysed with an atomic force microscope. The chemical state and elemental distribution of (Ti,A1)N films after oxidation were evaluated with X-ray photoelectron spectroscopy (XPS) and secondary-ion mass spectroscopy (SIMS). The colours of the oxidized films were interpreted with L*, a* and b* colour coordinates. The relationship between composition and the film stress was discussed, and the effects of the film composition on the oxidation behaviours of (Ti,A1)N films were also investigated.

2. Experimental procedures
TiN and magnetron designated deposition (Ti,A1)N films were prepared by reactive r.f. sputtering. The substrate was a tool steel as A2. Details of TiN and (Ti,AI)N film were reported elsewhere [11]. After depos-

C-T. Huang, J.-G. Duh/Surfaceand Coatings"Technology81 (1996) 164-171

ition, the stress and oxidation behaviours of the (Ti,A1)N films were analysed. The evaluation of film stress was carried out with a stress measurement system (FSM8800, Frontier, USA). A laser optical lever was employed to measure the change of curvature induced in the sample due to the deposited film. A clean, undeposited blank sample substrate was first measured prior to film deposition. The data were then compared with those taken after film deposition. The point-by-point subtraction data were fitted with a straight line where the slope was inversely proportional to the radius of curvature of the sample. The film stress S was calculated by the following equation [ 12]: SE(D) ~

165

For the investigation of chromaticity in the thin film due to the oxidation, the colour coordinates L*, a* and b* of (Ti,A1)N films after oxidation were further measured using a luminescence spectroscope (Photal, Otsuka Electronics, Japan) with a photodetector (MCPD-100, Otsuka Electronics, Japan). The illumination was from a D65 standard source and the field was 2 . The colour of oxidized (Ti,A1)N films can be represented with L*, a* and b* colour coordinates. L* represents the brightness. The positive and negative values of a* indicate red and green, respectively; and the positive and negative values of b* correspond to yellow and blue colour, respectively. The origin of the a* and b* axes means the colourless coordinate.

6(1 - v)RT

(1) 3. Results and discussion

where E is the Young's modulus of the substrate, v is the Poisson's ratio of the substrate, D is the thickness of the substrate, R is the net radius of curvature and T is the thickness of the film (T<< D). Oxidations of (Ti,A1)N coatings were carried out by heating the samples at 600 C in a 20%Oz-80%N2 atmosphere for 6 h. The furnace was a radiation heating quartz tube (E-45P, ULVAC, Japan). The infrared radiation was generated from an infrared lamp and then focused on the samples. The average heating and cooling rate was 100 C min 1 and the gas flow rate was 100 cm 3 m i n - 1. The structure of the coating after oxidation was analysed with an X-ray diffractometer (Mxpl8, Mac Science, Japan) by the grazing-incidence technique. The specimens were fixed at a grazing angle of 0.5 with respect to the incident X-ray beam. Through the grazing incidence, the relative intensity of the film is increased and more information concerning the film structure is obtained. Thus the grazing-incidence method is suitable to characterize the coating after oxidation. The surface morphologies of (Ti,A1)N coatings before and after oxidation were studied with an atomic force microscope (AST-CESMEX, CSEM, Switzerland). A sharp tip mounted on a small spring, i.e. cantilever, is pulled over the sample surface. A laser beam is deflected on the back of the mirror-like cantilever into a foursegmented photodiode which detects the intensity of the reflected laser light. The chemical state of the (Ti,A1)N coating assembly after oxidation was analysed by XPS (PHI1600, PerkinElmer, USA). In order to analyse the chemical state of the inner structure of the oxidized layer, an alternating sputtering technique was also employed. In addition, the elemental distributions of the oxidized coating in the direction perpendicular to the sample surface were studied with SIMS (IS-4f, Camera, France). The primary ion source was O~- with an accelerating voltage of 8 kV and a current of 250 nA.

3.1. Film stress of ( Ti, Al ) N films

The film stress of the as-deposited films was analysed by comparing the substrate curvature prior to deposition with that after deposition. Fig. 1 indicates the substrate bows of TiN and Tio.61Alo.39N coatings. The net radii of curvature from Fig. 1 were - 1 3 . 8 m and 7.8 m for TiN and Tio.61Alo.39N, respectively. According to Eq. (1), the residual stresses developed in TiN and Ti0.61Alo.39N are - 3 . 4 x 10a G P a and 4.1 x 103 GPa, respectively. This indicates that, with the addition of 39 tool% of A1N into the TiN unit cell, the originally compressive residual stress of the as-deposited TiN film becomes tensile for Tio.61Alo.39 coating. Generally N speaking, many factors would affect the residual stress of deposited films, such as thermal expansion mismatch, structure mismatch and deposition process. Since both TiN and Tio.61Alo.39N are deposited under the same conditions and also exhibit identical B1 f.c.c, structure [ 11 ], it is argued that the difference in thermal expansion coefficient between TiN and A1N leads to the tensile stress developed in Tio.61Alo.39N. A1N is a covalent compound, while TiN is a metallic compound. In general, a covalent compound has lower thermal expansion coefficient than a metallic compound [13]. From the literature, the thermal expansion coefficient of A2 steel is 12.9 x 10 -6 K -1 [14] and those of A1N and TiN are 5.7 x 10 -6 K -1 and 9.4 x 10 -6 K -x, respectively [13]. The addition of A1N into a TiN cell reduces the thermal expansion coefficient of the coating and thus introduces more thermal mismatch between the coating and the substrate. Hence the residual stress of the Tio.61Alo.39N coating tends to be tensile.

3.2. Oxidation behaviour of (Ti, Al ) N films

The grazing-incidence technique was employed to characterize the scales of a (Ti,A1)N coating after oxida-

166

C.-T. Huang, J.-G. Duh/Surface and Coatings Technology 81 (1996) 164 171

TiN

~z
0
,.,,

o
U3

-2

-4 -6
Ti0.61A[ 0.39N

-8

I0
X - Substrate (mm)

15

20

Fig. 1. Substrate bows of TiN and Tio.61Alo.39N coatings after deposition.

tion. Owing to the increase of the X-ray path in films caused by use of the grazing method, the relative intensity of the films is enhanced while that of the substrate is decreased. The X-ray diffraction patterns of the TiN and (Ti,A1)N coatings after oxidation at 600 C for 6 h are shown in Fig. 2. Since the TiN film is oxidized and then spalled off during heating at 600 C, there exist no peaks of Ti-containing oxide in the X-ray diffraction pattern. The diffraction peaks of the TiN-coated assembly after oxidation are identified only to be Fe-containing

oxides, such as F e 2 0 3 and F e 3 0 4 , as indicated in Fig. 2, curve a. TiN coatings tend to be oxidized at temperatures beyond 500 C and a poorly adherent and brittle layer of ruffle phase T i O 2 is formed [15]. The reaction from TiN to TiO2 is associated with a large volume expansion and consequently spalling is observed [16]. Thus pure TiN coating fails to provide adequate oxidation resistance for the substrate up to 600 C. In the case of (Ti,A1)N coatings, as 27 mol% of A1N is added to the TiN, i.e. for Tio.73A10.27N, n o spallation

Fe304 A TiO2
.

0 Fe203 El AIN

II Ti203 (Ti,AI)N

t i

(a)

n~
. oa a~ .~ o , aA Co)

g
& o
. , , o (c)

o
~ . ~ / [ L ~ a ~ .
~...'~ ~- - ~ . ~ , , ~ ~-~,...... ,;~.-~.. :___- - ,

"

(d)

~ l , , ~ l il i

d 25.0

k.Xnl

" ~.0

" 45.0 fiO. O 55.0 W,O IS.O 70.0 75.0 BO, O

30.0

35.0

2e A n g l e

Fig. 2. X-ray diffraction patterns of (Ti,AI)N films after oxidation obtained by the grazing-incidence method: curve a, TiN; curve b, Tio.v3Alo.2vN; curve c, Tio.61Alo.39N; curve d, Tio.sAlo.sN; curve e, Tio.4zAlo.ssN.

C-T. Huang, Z-G. Duh/Surface and Coatings Technology 81 (1996) 164-171

167

or cracking is observed on the coating surface. There still exist diffraction peaks of (Ti,A1)N, as indicated in Fig. 2, curve b. The addition of A1 atoms promotes the oxidation resistance of the (Ti,A1)N coating in comparison with TiN. In addition to the peaks of (Ti,A1)N, phases of titanium oxide, such as TiO 2 and T i 2 0 3 , and small peaks of Fe203 show up along with a diffraction pattern attributable to A1N. When the A1N mole percentage in (Ti,A1)N is increased, for example in the coatings of Tio.61Alo.39N and Tio.sAlo.sN, the majority of the peaks are associated with (Ti,A1)N and small amounts of titanium oxides and iron oxide are detected. It appears that the intensity of oxides relative to (Ti,A1)N is decreased with increasing A1 content. As the A1N mole percentage is further increased to 58%, peaks of (Ti,A1)N and the Fe substrate are observed, while peaks of Fe203 and TiO 2 are absent except a small peak of Ti203, as indicated in Fig. 2, curve e. It is apparent that the anti-oxidation of the (Ti,AI)N films is increased with the increase of the A1 content. The atomic force microscopy (AFM) surface topography of as-deposited and oxidized (Ti,A1)N films is shown in Fig. 3. It seems that the sizes of Tio.v3A10.2~N and Tio.sAlo.sN grains before oxidation are small and their distribution is rather uniform, as indicated in Figs. 3(a)

and 3(b). In contrast, the grains of (Ti,A1)N films after oxidation appear not uniform and the sizes are larger than those before oxidation, as shown in Figs. 3(c) and 3(d). This is attributed to the formation of oxide scales after oxidation treatment; thus larger grains are observed on the surface. Furthermore, the surface topography of the oxidized Tio.sAlo.sN film is much smoother than that of Ti0.73Alo.zvN. As described above in the section about the X-ray diffraction results, the oxidation resistance of (Ti,A1)N is increased with increase of A1 content. Thus the surface of the less oxidized Tio.sAlo.sN looks smoother. XPS was further employed to study the oxidation behaviours of the (Ti,A1)N films. Figs. 4 and 5 show the binding energies of A1 2p, Ti 2p, O ls, and N ls for Tio.v3Alo.27N and Tio.sAlo.sN coatings after oxidation, respectively. For both Tio.v3Alo.zvN and Tio.sAlo.sN, the binding energy of A1 2p pertains to that of A1203, while the binding energy of Ti 2p is attributed to TiO 2. According to Figs. 4(c) and 5(c), no clear peaks of N ls are detected. Hence the near surface of the (Ti,A1)N coating after oxidation is a mixture of TiO2 and A1203. Owing to the formation of the amorphous A1203, there are no apparent peaks of alumina in the X-ray diffraction patterns. From the phase diagram of Ti-A1-O [17,18], TiOz and A1203 are mutually insoluble and do not form

Fig. 3. AFM surface morphology of as-deposited and oxidized (Ti,A1)N films: (a) as-deposited Tio.73Alo.27N; (b) as-deposited Tio.sAlo.sN; (c) oxidized Tio.v3Alo.zTN;(d) oxidized Tio.sAlo.sN.

168

C- T. Huang, J.- G. Duh/Surface and Coatings Technology 81 (1996) 164 171

(a)

50O( G
O

'

'

~Ti 2P(3'/2)
600C
(.D

(b)

~ 400C

4000

c 300C

200C

-47

-450 -495 -4go -495 -450

Binding Energy (eV)

-90

-8's

-sb

-7~

-70

-65

Binding Energy (eV) (d)

(c)
D_ 270C D >.

>,
E

_.~ 260C

m
0

-411

--405

--4~

Binding Energy (eV)

--395 --390 -385

-545

-5~.o

-5~5

-5~o

-525

Binding Energy (eV)

Fig. 4. Binding energy of a Tio.73Alo.27N surface after oxidation: (a) Ti 2p; (b) A1 2p; (c) N Is; (d) O ls.

(a)

8OOO
n [)

ATi2P{:

5000I

(b)

'~

A[2P

v 6000

E
c

4000 2000
-475 -zJ~O

Cool
200q-

-450

10001

-9o
xlO4 (d)

-is

4'0

-75

-70

-65

Binding Energy (eV)

, , , i

Binding Energy (eV)

2500

>,
2400

2300 -41(

I~05

1400

-395I

--390

385

-545

Binding Energy (eV)

-540 -535 -530 - 525 Binding Energy (eV)

Fig. 5. Binding energy of a Tio.sAlo.sN surface after oxidation: (a) Ti 2p; (b) A1 2p; (c) N ls; (d) O ls.

ternary compounds below 1423 K [16]. Ichimura and Kawana reported that, in the first stage of oxidation of (Ti,A1)N film, Ti and A1 ions in the films were oxidized simultaneously and then formed the rutile and amorphous alumina [ 16]. In order to study the chemical state of the underlayer, an alternating sputtering method of XPS was employed. For every cycle, the surface of the coating was sputtered with Ar + ions for 3 min and then the XPS was performed. Fig. 6 shows the Ti 2p binding energy of Tio.v3A10.27N films after oxidation for various sputtering cycles. The presence of the binding energy of Ti 2p

implies that TiO2 was formed on the near surface. As the surface was sputtered with Ar + ions for 12 min, the peak related to Ti 3+, i.e. TiN, showed up. This is attributed to the unoxidized (Ti,A1)N coating. The elemental depth profiles of the (Ti,A1)N films after oxidation were analysed with SIMS. The depth profiles of (Ti,A1)N films with various compositions after oxidation are shown in Fig. 7. As indicated in Fig. 7(a), it seems that the elemental distribution of Tio.v3Alo.zTN after oxidation is not uniform. Drastic increases in aluminium and oxygen are observed on the outer layer of the coating after oxidation, while the intensity of

C.-T. Huang, J.-G. Duh/Surface and Coatings Technology 81 (1996) 164 171

169

8.53C

Ti. 4

6.634

T~ .3

0.9/*8

470 4~8 ~+6

&2

~o

~8

~&

~~ ~,2 ~o

Binding Energy (eV)

Fig. 6. Ti 2p binding energy of Tio.TsAlo.27N after oxidation by the alternating sputtering method.

nitrogen is decreased. For the oxidation of (Ti,A1)N films, the nitrogen desorbs and the (Ti,A1)N film loses its metastability. Ti ions are oxidized to form futile, while A1 ions diffuse outwards and form the oxide scales It is argued that an unoxidized (Ti,A1)N layer is adjacent to the substrate. Underneath the surface there exists an oxide layer of 0.2 pm thickness containing A1, Ti, O and N adjacent to the unoxidized (Ti,A1)N coating. As described in the XRD results, apart from the major peaks of (Ti,A1)N, there are peaks of titanium oxide and also peaks attributable to A1N. This reveals that titanium oxides are formed in the outer layer of Tio.73Alo.zTN after oxidation. The peaks of A1N are attributed to the formation of aluminium oxynitride. Perera reported an A1N and spinel structure in the A14.oOa.sN3.0 compound [-18]. The oxide scale of the outer layer in Tio.v3Alo.zvN after oxidation is a mixture of titanium oxides and aluminium oxynitride. Fig. 7(a) also indicates an increase of iron intensity around 0.1 pm from the surface region
1E+7

1E+7

(a)
1E+6 1E+5
\\

1E+6 1E+5

(c)

~ 1E+4
c 0

,-,AI ,. . . . . . . . .

-.
"',,.,. ...... ,....

1E+4 1E+3 1E+2

,.'~f-.

O 1E+3 1E+2 1E+1 1E+0

Fe

,,-

"~\

,,

~N

,~ ':'""'.."V"."

1E+1 1E+0

0.1

0.2

0.3

0.4

0.5

0.1

0.2

0.3

0.4

0.5

Depth (microns)

Depth (microns)

1E+7 1E+6 1E+5

1E+ 7

(d)
1E+6

Ti

--.\
,\

i
, ,"At,-'-,.,. " ..... i~" ":"

(b)

1E+5

~ 1E+4
0

1E+4
.-AI
O

U 1E+3 1E+2 1E+1 1E0 0 0.1 0.2 0.3 0.4 0.5

O 1E+3 1E+2

/N

\"

"1" "

1E+1 1E+ 0

0.1

0.2

0.3

0.4

0.5

Depth (microns)

Depth (microns)

Fig. 7. SIMS depth profiles of (Ti,A1)N films after oxidation: (a) Tio.73Alo.27N; (b) Tio.61Alo.39N; (c) Tio.sAlo.sN; (d) Tio.42Alo.58N.

170

C.- T. Huang, J.- G. Duh/Surface and Coatings Technology 81 (1996) 164 171
25 20 15 10 5
I
o '

of the oxidized layer. During oxidation, the diffusion of iron from the substrate through the grain boundary or pinholes results in the enrichment of iron on the surface. Similar results were found by Louw et al. [19]. In this study peaks of Fe203 are observed in the diffraction pattern, as indicated in Fig. 2. When the A1N mole percentage is increased to 39%, the thickness of the Al-rich and O-rich scale is decreased to 0.12pam, which is nearly half of that for the Tio.73Alo.zvN film. Furthermore, the diffusion layer of iron underneath the surface is also decreased to around 0.08 gin. When the A1N mole percentage is further increased to 50% and 58%, the scale thickness is decreased to 0.08 gm and 0.06 gm, and the diffusion layer of iron is reduced to 0.05 lam and 0.04 lain, respectively. A rather uniform elemental distribution of unoxidized (Ti,AI)N is, however, observed. This indicates that, with increasing aluminium content of (Ti,A1)N films, the scale thickness and the diffusion of iron through the coating is decreased. As described in the XRD results, the relative intensity of Fe20 3 is decreased with increasing A1 content and there are no clear peaks of iron oxides in the Tio.42A10.58N coating. This is attributed to the decrease of iron diffusion as the A1 content is increased. As a consequence the oxidation resistance of the (Ti,A1)N films is improved.

I
i

-5 -10 -15

--a
; e
II

-20 -25 -25

,ll I ]l I~i III/lllli! Iillll~llll[lll

-20

-15

-10

-5
[ a*]

0
-25 -- 25

10

15

20

25

Fig. 8. Colour coordinates a* and b* for (Ti,A1)N films after oxidation: a, TiN; b, Tio.73Alo.27N; c, Tio.61Alo.39N; d Tio 5Alo sN; e, Tio.42Alo.58N: w, colourless.

3.3. Colour of (Ti, Al )N films after oxidation

The colour of (Ti,A1)N films can be represented with L*, a* and b* colour coordinates. L* stands for the brightness. The positive and negative values of a* indicate red and green, respectively, while the positive and negative values of b* correspond to yellow and blue colour, respectively. The origin of the a* and b* axes means the colourless coordinate. The colour coordinate values of the films after oxidation are tabulated in Table 1 and the (a*,b*) coordinates are shown in Fig. 8. The values prior to oxidation are also indicated in Table 1 for comparison. Before oxidation the brightness values of both TiN and (Ti,A1)N range from 50 to 60. In fact, the brightness of the (Ti,A1)N films after oxidation is nearly identical to that before oxidation due to the anti-oxidation characteristic of (Ti,A1)N films. On the other hand, the brightness of TiN film after oxidation
Table 1 Colour coordinate values of as-deposited and oxidized (Ti,A1)N films Film composition As-deposited films L* 60.9 57.2 56.4 53.8 56.4 a* 13.1 6.4 3.8 2.6 0.9 b* 13.2 -6.0 -7.3 -7.4 -6.8 Oxidized films L* 9.75 49.8 58.7 55.2 44.8 a* 1.0 - 13.8 4.1 4.5 8.3 b* -4.9 - 11.3 6.8 11.3 -20.2

is much lower than that of (Ti,A1)N, as indicated in Table 1. This is because iron oxides are formed on the surface of the TiN coating after oxidation. Thus the brightness of TiN films after oxidation is degraded. In addition, the colour changes significantly after oxidation for (Ti,A1)N film with lower A1 contents, such as in the cases of Tio.73Alo.zvN and Tio.6xAlo.39N films. The colour of the (Ti,A1)N film is red-blue before oxidation, as shown in Fig. 8. However, the colour of Tio.73Alo.zTN switches to green-blue and that of Tio.61Alo.39N turns to red yellow. As the A1 content is further increased, i.e. for Tio.sAlo.sN and Tio.42Alo.58N, the colour of films after oxidation is still in the red-blue field. Owing to the increase of anti-oxidation with the increase of A1 content, the (Ti,A1)N films with higher A1 contents after oxidation maintain the originally red blue colour tone.

4. Conclusions

TiN Tio.TsAlo.zTN Tio.61Alo.39N Tio.sAlo.sN Tio.42Alo.ssN

(1) (Ti,A1)N films were deposited onto A2 tool steel by reactive r.f. magnetron sputtering. With the addition of 39 mol% of A1N into the TiN unit cell, the originally compressive residual stress in the as-deposited TiN film turned tensile for the Tio.6xAlo.39N coating. (2) The TiN film was oxidized and then spalled off during heating at 600 C and iron-containing oxides were formed. For oxidation of (Ti,A1)N films, no spallation was observed and the majority of the phases were associated with the original (Ti,A1)N film along with small amounts of titanium oxides and iron oxides. For Tio.a2Alo.58N films after oxidation, only phases of (Ti,A1)N and TizO 3 were observed.

C - T . Huang, J.-G. Dub~Surface and Coatings Technology 81 (1996) 164-171

171

(3) The near-surface structure of the (Ti,A1)N coating after oxidation was a mixture of TiO2 and a m o r p h o u s A120 3. A drastic increase of A1 and oxygen was observed on the outer layer of the coating and an unoxidized (Ti,A1)N layer was adjacent to the substrate. During oxidation, the diffusion of iron from the substrate through the grain b o u n d a r y or pinholes resulted in the formation of iron oxides near the surface of (Ti,A1)N films. (4) The brightness of the (Ti,A1)N films after oxidation was nearly identical to that before oxidation, while that of T i N was m u c h lower than those of (Ti,A1)N films. Owing to the increase of the anti-oxidation characteristic with the increase of A1 content, the colour of (Ti,A1)N films with the higher A1 contents after oxidation remained red-blue. (5) The addition of A1 atoms p r o m o t e d the oxidation resistance of the (Ti,A1)N coating in comparison with pure TiN. As the A1 content was increased, the antioxidation of the (Ti,A1)N films was enhanced. The scale thickness and the diffusion of iron t h r o u g h the coating were, however, decreased.

References
[-1] Y.I. Chen and J.G. Duh, Surf. Coat. Technol., 48 (1991) 163. [2] J.G. Duh and J.C. Doong, Surf. Coat. Technol., 56 (1993) 257. 1-3] V.R. Parameswaran, J.-P. Immarigeon and D. Nagy, Surf. Coat. Technol., 52 (1992) 251. [4] F. Hohl, H.-R. Stock and P. Mayr, Surf. Coat. TechnoL, 54 55 (1992) 160. I-5] W.D. Munz, J. Vac. Sci. TechnoL A, 4(6) (1986) 2717. [6] T. Ikeda and H. Satoh, Thin Solid Films, 195 (1991) 99. [7] O. Knotek, W.D. Munz and T. Leyendecker, J. Vac. Sci. Technol. A, 5(4) (1987) 2173. I-8] H. Freller and H. Haessler, Surf Coat. TechnoL, 36 (1988) 219. 1-9] C.T. Huang and J.G. Duh, Surf. Coat. TechnoL, 56 (1992) 51. [10] J.G. Duh and C.T. Huang, Surf. Coat. TechnoL, 56 (1992) 61. [11] C.T. Huang and J.G. Duh, Surf. Coat. Technol., 71 (1995) 259. [12] Instruction Manual, Frontier Semiconductor Measurements, Inc., USA. [13] H. Holleck, Surf. Coat. Technol., 43 44 (1990) 245. [14] W.H. Cubberly, P.M. Unterweiser, D. Benjamin, C.W. Kirkpatrick and K. Nieman, Metals Handbook, 9th edn, Vol. 3, American Society for Metals, Metals Park, OH, 1980, p. 441. 1-15] W.D. Munz, Werkst. Korros., 41 (1990) 753. 1-16] H. Ichimura and A. Kawana, J. Mater. Res., 8(5) (1993) 1093. [17] S.M. Lang, C.L. Fillmore and L.H. Maxwell, J. Res. Natl. Bur. Stand., 48 (1952) 298. [18] D.S. Perera, Br. Ceram. Trans. J., 89 (1990) 57. [19] C.W. Louw, I.L. Strydom and K. van den Heever, Surf. Coat. Technol., 49 (1991) 348.

Acknowledgement
This work is supported by the N a t i o n a l Science Council, Taiwan, under Contracts NSC83-0405E007-029 and NSC84-2216-E007-012.