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Surface & Coatings Technology 201 (2006) 4411 – 4418

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A study of AC reactive magnetron sputtering technique


for the deposition of compositionally graded
coating in the Cr–Al–N system
Syamala Rani Pulugurtha, Deepak G. Bhat ⁎
Department of Mechanical Engineering, University of Arkansas, Fayetteville, AR 72701, United States
Available online 1 November 2006

Abstract

Cr1−xAlxN coatings were deposited on various substrates using an inverted cylindrical AC magnetron sputtering system with chromium and
aluminum targets, at a chamber pressure of 0.2 Pa (1.5 mTorr) for 1.5 h. The present study focuses on the effect of various deposition parameters,
such as the N2/Ar ratio and the target power on the properties of the coatings obtained. Some of the samples were subjected to oxidation in still air
at 900 °C. The morphology and structure of these coatings were investigated by various analytical techniques such as XRD, SEM, EDAX and
EDS. We report on the effect of processing parameters on the morphology, orientation, composition and oxidation behavior of the compositionally
graded (Cr1−xAlx)N coatings.
© 2006 Published by Elsevier B.V.

Keywords: Physical vapor deposition (PVD); CrAlN; CrN; Morphology; Phase analysis; Oxidation

1. Introduction 2. Experimental

Chromium based coatings such as CrNx and Cr1−xAlxN are 2.1. Film deposition
promising hard films in applications such as die casting molds,
metal forming, machining and in combined wear and corrosion. The deposition was carried out in an inverted cylindrical mag-
Considerable research has been carried out in determining the netron sputtering system, consisting of two cylindrical 10-cm
phase transition of Cr–Al–N films deposited by various PVD high targets with an inner diameter of 33 cm, placed in the cham-
methods. Also, the oxidation studies indicate the superiority of ber wall with a spacer that separates them from each other (Fig. 1).
Cr–Al–N films over Ti-based coatings with the formation of A mid-frequency AC power supply operating at 41 kHz provides
complex aluminum and chromium oxides, which eventually
suppress diffusion of oxygen in the bulk [1–9]. Recently, some
researchers have shown that coatings such as CrN, TiAlN, and
Cr2O3 can be used as suitable epitaxial templates for the growth
of α-alumina [10,11]. The aim of this work was to study the
deposition and oxidation behavior of PVD CrNx and Cr1−xAlxN
films for possible use as intermediate template layers for multi-
layered alumina coatings. We have investigated the influence of
target power and Ar:N2 flow ratio during deposition on the
morphology and oxidation behavior of the Cr1−xAlxN and CrNx
films.

⁎ Corresponding author.
E-mail address: dbhat@nsf.gov (D.G. Bhat). Fig. 1. Schematic of ICM-10 system.

0257-8972/$ - see front matter © 2006 Published by Elsevier B.V.


doi:10.1016/j.surfcoat.2006.08.079
4412 S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418

Table 1
Deposition parameters
Target power (kW) 3, 5, 6.5
Substrate power (W) 500
Gas flow rates (sccm) Ar 43:N2 43; Ar 60: N2 40; Ar 70: N2 30
Base pressure 1.0 × 10− 5 Torr (1.3 × 10− 3 Pa)
Deposition pressure 1.5 mTorr (0.2 Pa)
Deposition time, s 5400 s
Substrates 316 stainless steel, tungsten carbide, glass

the sputtering power, such that each target behaves alternately as a


cathode and an anode during each cycle. This unique arrangement
permits deposition of insulating films without charging or target
poisoning, when the reactive gas ratios are properly controlled.
Two plasma-sprayed Cr targets were used for depositing CrNx
coatings. 99.5% pure Cr was plasma-sprayed on to the inner Fig. 2. A plot between sample position and resistance.
surfaces of 304 SS backing rings. For the deposition of Cr1−xAlxN
films, one of the Cr targets was replaced by an Al target. CrN–
Cr2N and Cr1−xAlxN films were deposited on various substrates. were also analyzed by X-ray diffraction (XRD) to determine the
Samples for CrN deposition were set horizontally on the fixture phase composition and orientation using a Ni-filtered CuKα X-
plate, close to the bottom target, whereas samples for Cr1−xAlxN ray source. The electrical resistance of the films was measured
coating were placed vertically along the chamber axis, to with a digital multimeter, using the two-probe method.
determine the composition gradient expected during deposition.
Prior to deposition, the samples were ultrasonically cleaned for 3. Results and discussion
30 min in standard alcohol based chemicals. The detailed de-
position conditions are listed in Table 1. The coatings were The Cr1−xAlxN films deposited on glass were highly adherent
deposited at varying target powers and Ar:N2 ratios for 90 min at a as compared to those on stainless steel substrates, while the CrNx
chamber pressure of 0.2 Pa (1.5 mTorr). It was discovered after the films showed good adhesion on all the substrates. Therefore, an
films were analyzed that the chamber had developed a minute leak initial layer of TiN was deposited for about 30 min to improve
in the OES port. This prevented the chamber from achieving a the adhesion of Cr1−xAlxN films on steel in the subsequent
base pressure of lower than 1.3 × 10− 3 Pa. After the port was experiments.
cleaned and reassembled, the vacuum level improved by more Fig. 2 shows the variation of electrical resistance of the
than an order of magnitude to a base pressure of 6.5 × 10− 5 Pa. coatings, as a function of position along the chamber axis, for
Thus, as described in the following, the deposited films contained the films deposited at 5 kW and different Ar:N2 flow rates.
a much higher concentration of oxygen than desired or anticipated. Samples close to the chromium target (position 1) showed low
resistance (in ohms), while those close to the aluminum target
2.2. Oxidation studies (position 5) showed resistance in mega ohms, indicating in-
sulating character. As the concentration of aluminum in the film
The Cr1−xAlxN coatings on steel samples were annealed in a increased, the metallic character in the film reduced signifi-
horizontal tube furnace at 900 °C in still air for 6 h. Table 2 lists cantly. Table 3 shows the aluminum contents of coatings
the samples that were analyzed for oxidation studies. deposited at 5 kW at different sample positions. As the Al
content increases, the AlN content is expected to increase,
2.3. Characterization of films leading to an increase in the electrical resistance of the film. It
should be noted that all the films have a relatively high oxygen
The coatings were characterized using scanning electron content, and thus the metallic character of films close to the Cr
microscopy (SEM). The film composition was determined by target is most likely due to a lower Al (and therefore AlN)
the energy-dispersive X-ray (EDAX) technique. The coatings content.

Table 2
Coating compositions and oxidation parameters
Sample # Composition, at.% Power (kW) Ar/N2 (sccm) Annealing temp (°C) Time (h)
Cr Al N O
79ss1 44.60 1.14 35.05 19.20 3 70–30 900 6
79ss5 19.42 23.08 29.33 28.17 3 70–30 900 6
78ss1 43.25 0.90 36.36 19.50 3 60–40 900 6
78ss5 20.55 25.27 25.99 28.19 3 60–40 900 6
77ss1 43.02 0.92 37.89 19.35 3 43–43 900 6
77ss5 19.05 24.83 27.89 28.07 3 43–43 900 6
S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418 4413

Table 3 spectively, are close to the chromium target, and show well
Sample position versus Al concentration in Cr1−xAlxN films defined islands of crystals. As the power increases, the films
Sample position Al concentration (at.%) Al concentration (mol%) tend to become more continuous and featureless. The com-
1 1.5 1 positions of these films, as determined by the EDAX technique,
2 1.9 1.4 showed 40 at.% Cr, 1.5 at.% Al, 38 at.% N, and 18 at.% O near
3 3 3 the chromium target, irrespective of the variation in the target
4 12 11
power. As the sample position moves toward the aluminum
5 23 26
target, the amount of Al in the film gradually increases. For
example, samples 3(b) and 3(c) show Al contents of 2 at.% and
3.1. Microstructure characterization 3 at.%. Fig. 3(d) and (h) show the microstructure of films closer to
the aluminum target with compositions of 31 at.% Cr, 12 at.% Al,
The morphology of films deposited at different sputtering 40 at.% N, 17 at.% O. With reference to Fig. 2, these films
powers and gas flow rates of 70 sccm Ar and 30 sccm N2 is represent positions 1 through 4 respectively for 3(a) through 3(d)
shown in Fig. 3. The morphologies varied along the length of the at 3 kW, and 3(e) through 3(h) at 5 kW. The sample closest to the
substrate holder. Since the two targets are placed one above the Al target (which was later used in the oxidation experiment)
other, the concentration of ionized metal species (Al3+ and Cr3+) showed an Al content of about 23 at.%. As the aluminum content
is expected to vary along the vertical axis of the chamber. in the film increases, the film structure becomes finer and conti-
Secondly, the samples in this case were suspended vertically at nuous with a small crystallite size at both the sputtering powers.
different heights between the two target rings. Thus, the It has been shown by Creus, et al. [12] that incorporation of
orientation of the substrate surface in this case was perpendi- nitrogen in the Al–Cr coatings reduces the concentration of Al in
cular to the flux of ionized species. The substrate orientation the film. Fig. 4(a)–(d) show the micrographs of Cr1−xAlxN films
influences the growth mode of the films, and the variation in the deposited at 3 kW and Ar:N2 flow rates of 70:30 and 60:40 sccm,
plasma composition permits deposition of compositionally respectively. The films obtained near the chromium target,
graded Cr1−xAlxN films. samples 4 (a) and (c), showed highly columnar morphology at
Fig. 3(a)–(h) show the SEM micrographs of Cr1−xAlxN both the Ar:N2 ratios due to the low Al content. By comparison,
coatings at Ar:N2 flow rates of 70:30 sccm at 3 kW and 5 kW, samples 4(b) and 4(d) showed a relatively smooth structure, as
respectively. Samples 3(a) and 3(e), at 3 kW and 5 kW re- the concentration of the Al in the film increased. We observe that

Fig. 3. (a)–(d) SEM micrographs at 3 kW and Ar:N2 flow rates of 70:30 sccm. (a) 1 mol% Al (b) 1.4 mol% Al (c) 3.5 mol% Al (d) 11 mol% Al; (e) –(h): at 5 kW and
Ar:N2 flow rates of 70:30 sccm. (e) 1 mol% Al (f ) 1.4 mol% Al (g) 3.5 mol% Al (h) 11 mol% Al.
4414 S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418

Fig. 4. SEM micrographs of Cr1−xAlxN film deposited at 3 kW and Ar/N2 flow rates of 60–40 sccm (a) close to Cr (b) close to Al, and 70–30 sccm (c) close to Cr (d)
close to Al.

Fig. 5. SEM micrographs of CrNx coatings at 5 kW with Ar–N2 flow (sccm) (a) 43–43 (b) 60–40 (c) 70–30.

Fig. 6. XRD spectra of Cr1−xAlxN deposited at 3 kW and Ar/N2 flow rate of 60–40 sccm.
S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418 4415

an increase in the N2 partial pressure in the chamber tends to For CrNx, the substrates were placed horizontally on the
make a denser coating, while an increase in the Al content of the substrate holder such that the flux of the species was parallel to
film tends to form a smoother, less columnar film. the substrate. This is expected to influence the film morphology,
Fig. 5(a)–(c) show the SEM micrographs of CrNx coatings at by influencing the growth mode. We observe a predominantly
Ar:N2 flow rates of 43:43, 60:40, and 70:30 sccm at 5 kW, columnar growth mode in our films. In addition, the EDAX
respectively. It can be clearly seen that Ar:N2 flow rates during analysis showed that there was a significant amount of oxygen
deposition can strongly affect the morphology of the CrNx in the coatings, and the films were actually Crx(O,N)1−x.
coatings. A very porous and columnar grain structure is produced
at an Ar:N2 ratio of 43:43 sccm (Fig. 5a). At the Ar:N2 flow rate of 3.2. Phase analysis
60:40 sccm (Fig. 5b), the film is coarser and slightly denser. As the
nitrogen flow rate was further decreased, the film showed a dense Fig. 6 shows the XRD peaks of the Cr1−xAlxN films
“cauliflower” structure (Fig. 5c). An increase in the nitrogen deposited at 3 kW target power and Ar:N2 flow rate of
concentration during deposition was found to give rise to a more 60:40 sccm. In this study, the film composition varied from
dense structure [13–15]. about 1 mol% Al to 26 mol% Al along the sample position in

Fig. 7. XRD spectra of (a) CrNx, (b) Cr1−xAlxN close to the Cr target and (c) Cr1−xAlxN close to the Al target, after oxidation at 900 °C.
4416 S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418

the substrate holder. It is predicted that the crystal structure for is high enough to cause the formation of Cr2O3 in the film during
the pseudo-binary Cr1−xAlxN changes from B1 type (FCC) to the deposition. But the chromium to nitrogen ratio in all the films
B4 (Wurtzite) type at about 77 mol% AlN [16–19]. From the is approximately 1:1, which is close to stoichiometric CrN.
XRD results, pseudo-binary Cr–Al–N films were identified to
be the B1 type crystal structure for all samples, as the films were 3.3. Oxidation studies
rich in CrN. In addition to the peaks originating from the steel
substrates, the diffraction peaks of planes {111}, {200}, and The oxidation behavior was studied for CrNx and Cr1−xAlxN
{400}, corresponding to the CrN phase are identified, although films. The samples deposited at 3 kW and different Ar:N2 flow
the existence of Cr2N phase cannot be excluded due to the peak rates withstood the annealing temperature of 900 °C in air for
overlap. The B1 crystalline phases in the films deposited at 6 h. XRD patterns after annealing at 900 °C are shown in Fig. 7.
3 kW and Ar:N2 flow rate of 60–40 sccm showed a (111) Fig. 7(a) shows data for CrN and Fig. 7(b) and (c) for Cr1−xAlxN
preferred orientation. An increase in the Al content in the films at 3 kW and Ar:N2 flow rate of 60–40 sccm.
caused the peaks to shift to higher diffraction angles. The The CrNx coating manifests clear signs of oxidation at
XRD analysis showed the presence of Cr2O3 peaks, indicating 900 °C with the presence of peaks of α-Cr2O3, with a strong
that the films contain multiple phases. The formation of chro- (110) preferred orientation, as shown in Fig. 7(a). On the other
mium oxynitrides cannot be ruled out, as indicated by the peak hand, the Cr1−xAlxN samples show several CrN peaks even after
shifts. oxidation, indicating an improvement in the thermal stability up
From the EDAX analysis, it was observed that all the films to 900 °C as observed from the XRD analysis. These results are
(CrNx or Cr1−xAlxN) contain more than 18 at.% of oxygen, which in good agreement with the results of earlier groups [1–9].

Fig. 8. SEM micrographs of Cr1−xAlxN films close to the Cr target (a) as-deposited (b) annealed in air; close to the Al target (c) as-deposited (d) annealed in air at
900 °C; and CrNx (e) as-deposited (f ) annealed in air at 900 °C.
S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418 4417

Fig. 9. SEM micrographs of Cr1−xAlxN films at 3 kW and different Ar:N2 flow rates: At 70:30 sccm: (a) close to Cr target (b) close to Al target; at 60:40 sccm: (c) close
to Cr target (d) close to Al target; at 43:43 sccm (e) close to Cr target (f ) close to Al target; annealed in air at 900 °C.

Fig. 8 shows the micrographs of the Cr1−xAlxN and CrNx more in concentration in the film at higher nitrogen flow rates as
films heated in air. The films show the evidence of densification can be seen from the Fig. 9(f ).
(sintering) and noticeable recrystallization. The films close to
the chromium target, shown in Fig. 8(a) and (c), have faceted 4. Conclusions
crystallites with hexagonal shape, while the films close to the
aluminum target do not show any well defined crystal 1. The composition of the Cr1−xAlxN films varied along the
morphology after heating in air to 900 °C. length of the chamber axis from about 1.14 at.% of Al to
Fig. 9(a)–(f ) show the micrographs of the Cr1−xAlxN films 23 at.% of Al at all the deposition conditions.
close to Cr and Al targets, deposited at 3 kW and Ar:N2 rates of 2. The CrN x films exhibit highly columnar growth mode
70:30, 60:40 and 43:43 sccm, and annealed in air at 900 °C. All when the substrate is oriented parallel to the flux of ion-
the films show densification as a result of sintering in air. As the ized species. By contrast, the Cr1−xAl xN films exhibit
nitrogen content in the films increases, samples close to the smoother morphology, with less pronounced columnar
chromium target show hexagonal crystal structure with a large habit, when the substrate is oriented normal to the flux of
crystallite size at Ar:N2 equal to 43:43, while for the samples ionized species.
close to the aluminum target, the films do not have a well 3. The CrNx coatings got oxidized to α-Cr2O3 on heating in air
defined crystal structure. Interestingly, there are some whiskers at 900 °C, while the Cr–Al–N films showed an improvement
observed on the films on oxidation in air. These whiskers were in thermal stability.
4418 S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418

Acknowledgements [7] J.L. Endrino, G.S. Fox-Rabinovich, C. Gey, Surf. Coat. Technol. 200 (2006)
6840.
[8] M. Brizuela, A. Garcia-Luis, I. Braceras, J.I. Onate, J.C. Sanchez-Lopez, D.
The authors acknowledge Alan Toland and Dr. John Shultz Martinez-Martinez, C. Lopez-Cartes, A. Fernandez, Surf. Coat. Technol. 200
of Arkansas Analytical Laboratory for their help with the (2005) 192.
analysis, and Dr. Atul Khanna, post-doctoral research associate, [9] J.C. Sanchez-Lopez, D. Martinez-Martinez, C. Lopez-Cartes, A. Fernan-
for his help during deposition experiments. The research was dez, M. Brizuela, A. Garcia-Luia, J.I. Onate, J. Vac. Sci. Technol., A, Vac.
Surf. Films 23 (4) (2005) 681.
funded by the National Science Foundation through Grant #
[10] T. Kohara, H. Tamagaki, Y. Ikari, H. Fujiii, Surf. Coat. Technol. 185 (2004) 166.
DMI-0400167. [11] M. Astrand, T.I. Selinda, F. Fietzke, H. Klostermann, Surf. Coat. Technol.
188–189 (2004) 186.
References [12] J. Creus, A. Billard, F. Sanchette, Thin Solid Films 466 (2004) 1.
[13] C.S. Lin, C.S. Ke, H. Peng, Surf. Coat. Technol. 146–147 (2001) 168.
[1] W. Kalss, A. Reiter, V. Derflinger, C. Gey, J.L. Endrino, 16th International [14] C. Liu, G. Bi, H. Ziegale, A. Leyland, A. Matthews, J. Vac. Sci. Technol.,
Plansee seminar, vol. 3, HM58, 2005, p. 136. A, Vac. Surf. Films 20 (3) (2002) 772.
[2] R. Franz, B. Sartory, R. Kaindi, R. Tessadri, A. Reiter, V.H. Derflinger, P. [15] A. Sugishima, H. Kajioka, Y. Makino, Surf. Coat. Technol. 97 (1997) 590.
Polcik, C. Mitterer, 16th International Plansee seminar, vol. 3, HM58, 2005, [16] Y. Makino, K. Nogi, Surf. Coat. Technol. 98 (1998) 1008.
p. 930. [17] M. Kawate, A. Kimura, T. Suzuki, J. Vac. Sci. Technol., A, Vac. Surf.
[3] O. Knotek, F. Loffler, H.J. Scholl, Surf. Coat. Technol. 45 (1991) 53. Films 20 (2) (2002) 569.
[4] J. Vetter, E. Lugscheider, S.S. Guerreiro, Surf. Coat. Technol. 98 (1998) 1233. [18] H. Hasegawa, M. Kawate, T. Suzuki, Surf. Coat. Technol. 200 (2005) 2409.
[5] M. Kawate, A.K. Hashimoto, T. Suzuki, Surf. Coat. Technol. 165 (2003) 163. [19] A. Reiter, V.H. Derflinger, B. Hanselmann, T. Bachmann, B. Sartory, Surf.
[6] O. Banakh, P.E. Schmid, R. Sanjines, F. Levy, Surf. Coat. Technol. 163–164 Coat. Technol. 200 (2005) 2114.
(2003) 57.