Surface & Coatings Technology 201 (2006) 4411 – 4418

www.elsevier.com/locate/surfcoat

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)
Substrate power (W)
Gas flow rates (sccm)
Base pressure
Deposition pressure
Deposition time, s
Substrates
3, 5, 6.5
500
Ar 43:N2 43; Ar 60: N2 40; Ar 70: N2 30
1.0 × 10− 5 Torr (1.3 × 10− 3 Pa)
1.5 mTorr (0.2 Pa)
5400 s
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
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.
Samples for CrN deposition were set horizontally on the fixture
plate, close to the bottom target, whereas samples for Cr1−xAlxN
coating were placed vertically along the chamber axis, to
determine the composition gradient expected during deposition.
Prior to deposition, the samples were ultrasonically cleaned for
30 min in standard alcohol based chemicals. The detailed de-
position conditions are listed in Table 1. The coatings were
deposited at varying target powers and Ar:N2 ratios for 90 min at a
chamber pressure of 0.2 Pa (1.5 mTorr). It was discovered after the
films were analyzed that the chamber had developed a minute leak
in the OES port. This prevented the chamber from achieving a
base pressure of lower than 1.3 × 10− 3 Pa. After the port was
cleaned and reassembled, the vacuum level improved by more
than an order of magnitude to a base pressure of 6.5 × 10− 5 Pa.
Thus, as described in the following, the deposited films contained
a much higher concentration of oxygen than desired or anticipated.
2.2. Oxidation studies
The Cr1−xAlxN coatings on steel samples were annealed in a
horizontal tube furnace at 900 °C in still air for 6 h. Table 2 lists
the samples that were analyzed for oxidation studies.
2.3. Characterization of films
The coatings were characterized using scanning electron
microscopy (SEM). The film composition was determined by
the energy-dispersive X-ray (EDAX) technique. The coatings
Fig. 2. A plot between sample position and resistance.
were also analyzed by X-ray diffraction (XRD) to determine the
phase composition and orientation using a Ni-filtered CuKα X-
ray source. The electrical resistance of the films was measured
with a digital multimeter, using the two-probe method.
3. Results and discussion
The Cr1−xAlxN films deposited on glass were highly adherent
as compared to those on stainless steel substrates, while the CrNx
films showed good adhesion on all the substrates. Therefore, an
initial layer of TiN was deposited for about 30 min to improve
the adhesion of Cr1−xAlxN films on steel in the subsequent
experiments.
Fig. 2 shows the variation of electrical resistance of the
coatings, as a function of position along the chamber axis, for
the films deposited at 5 kW and different Ar:N2 flow rates.
Samples close to the chromium target (position 1) showed low
resistance (in ohms), while those close to the aluminum target
(position 5) showed resistance in mega ohms, indicating in-
sulating character. As the concentration of aluminum in the film
increased, the metallic character in the film reduced signifi-
cantly. Table 3 shows the aluminum contents of coatings
deposited at 5 kW at different sample positions. As the Al
content increases, the AlN content is expected to increase,
leading to an increase in the electrical resistance of the film. It
should be noted that all the films have a relatively high oxygen
content, and thus the metallic character of films close to the Cr
target is most likely due to a lower Al (and therefore AlN)
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
Sample position versus Al concentration in Cr1−xAlxN films
Sample position Al concentration (at.%) Al concentration (mol%)
1 1.5 1 positions of these films, as determined by the EDAX technique,
2 1.9 1.4
3 3 3 the chromium target, irrespective of the variation in the target
4 12 11
5 23 26
3.1. Microstructure characterization
The morphology of films deposited at different sputtering
powers and gas flow rates of 70 sccm Ar and 30 sccm N2 is
shown in Fig. 3. The morphologies varied along the length of the
substrate holder. Since the two targets are placed one above the
other, the concentration of ionized metal species (Al3+ and Cr3+)
is expected to vary along the vertical axis of the chamber.
Secondly, the samples in this case were suspended vertically at
different heights between the two target rings. Thus, the
orientation of the substrate surface in this case was perpendi-
cular to the flux of ionized species. The substrate orientation
influences the growth mode of the films, and the variation in the
plasma composition permits deposition of compositionally
graded Cr1−xAlxN films.
Fig. 3(a)–(h) show the SEM micrographs of Cr1−xAlxN
coatings at Ar:N2 flow rates of 70:30 sccm at 3 kW and 5 kW,
respectively. Samples 3(a) and 3(e), at 3 kW and 5 kW re-
spectively, are close to the chromium target, and show well
defined islands of crystals. As the power increases, the films
tend to become more continuous and featureless. The com-
showed 40 at.% Cr, 1.5 at.% Al, 38 at.% N, and 18 at.% O near
power. As the sample position moves toward the aluminum
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 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,
40 at.% N, 17 at.% O. With reference to Fig. 2, these films
represent positions 1 through 4 respectively for 3(a) through 3(d)
at 3 kW, and 3(e) through 3(h) at 5 kW. The sample closest to the
Al target (which was later used in the oxidation experiment)
showed an Al content of about 23 at.%. As the aluminum content
in the film increases, the film structure becomes finer and conti-
nuous with a small crystallite size at both the sputtering powers.
It has been shown by Creus, et al. [12] that incorporation of
nitrogen in the Al–Cr coatings reduces the concentration of Al in
the film. Fig. 4(a)–(d) show the micrographs of Cr1−xAlxN films
deposited at 3 kW and Ar:N2 flow rates of 70:30 and 60:40 sccm,
respectively. The films obtained near the chromium target,
samples 4 (a) and (c), showed highly columnar morphology at
both the Ar:N2 ratios due to the low Al content. By comparison,
samples 4(b) and 4(d) showed a relatively smooth structure, as
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
make a denser coating, while an increase in the Al content of the
film tends to form a smoother, less columnar film.
Fig. 5(a)–(c) show the SEM micrographs of CrNx coatings at
Ar:N2 flow rates of 43:43, 60:40, and 70:30 sccm at 5 kW,
respectively. It can be clearly seen that Ar:N2 flow rates during
deposition can strongly affect the morphology of the CrNx
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
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
“cauliflower” structure (Fig. 5c). An increase in the nitrogen
concentration during deposition was found to give rise to a more
dense structure [13–15].
For CrNx, the substrates were placed horizontally on the
substrate holder such that the flux of the species was parallel to
the substrate. This is expected to influence the film morphology,
by influencing the growth mode. We observe a predominantly
columnar growth mode in our films. In addition, the EDAX
analysis showed that there was a significant amount of oxygen
in the coatings, and the films were actually Crx(O,N)1−x.
3.2. Phase analysis
Fig. 6 shows the XRD peaks of the Cr1−xAlxN films
deposited at 3 kW target power and Ar:N2 flow rate of
60:40 sccm. In this study, the film composition varied from
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
the pseudo-binary Cr1−xAlxN changes from B1 type (FCC) to
B4 (Wurtzite) type at about 77 mol% AlN [16–19]. From the
XRD results, pseudo-binary Cr–Al–N films were identified to
be the B1 type crystal structure for all samples, as the films were
rich in CrN. In addition to the peaks originating from the steel
substrates, the diffraction peaks of planes {111}, {200}, and
{400}, corresponding to the CrN phase are identified, although
the existence of Cr2N phase cannot be excluded due to the peak
overlap. The B1 crystalline phases in the films deposited at
3 kW and Ar:N2 flow rate of 60–40 sccm showed a (111)
preferred orientation. An increase in the Al content in the films
caused the peaks to shift to higher diffraction angles. The
XRD analysis showed the presence of Cr2O3 peaks, indicating
that the films contain multiple phases. The formation of chro-
mium oxynitrides cannot be ruled out, as indicated by the peak
shifts.
From the EDAX analysis, it was observed that all the films
(CrNx or Cr1−xAlxN) contain more than 18 at.% of oxygen, which
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.
is high enough to cause the formation of Cr2O3 in the film during
the deposition. But the chromium to nitrogen ratio in all the films
is approximately 1:1, which is close to stoichiometric CrN.
3.3. Oxidation studies
The oxidation behavior was studied for CrNx and Cr1−xAlxN
films. The samples deposited at 3 kW and different Ar:N2 flow
rates withstood the annealing temperature of 900 °C in air for
6 h. XRD patterns after annealing at 900 °C are shown in Fig. 7.
Fig. 7(a) shows data for CrN and Fig. 7(b) and (c) for Cr1−xAlxN
at 3 kW and Ar:N2 flow rate of 60–40 sccm.
The CrNx coating manifests clear signs of oxidation at
900 °C with the presence of peaks of α-Cr2O3, with a strong
(110) preferred orientation, as shown in Fig. 7(a). On the other
hand, the Cr1−xAlxN samples show several CrN peaks even after
oxidation, indicating an improvement in the thermal stability up
to 900 °C as observed from the XRD analysis. These results are
in good agreement with the results of earlier groups [1–9].
 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
films heated in air. The films show the evidence of densification
(sintering) and noticeable recrystallization. The films close to
the chromium target, shown in Fig. 8(a) and (c), have faceted
crystallites with hexagonal shape, while the films close to the
aluminum target do not show any well defined crystal
morphology after heating in air to 900 °C.
Fig. 9(a)–(f ) show the micrographs of the Cr1−xAlxN films
close to Cr and Al targets, deposited at 3 kW and Ar:N2 rates of
70:30, 60:40 and 43:43 sccm, and annealed in air at 900 °C. All
the films show densification as a result of sintering in air. As the
nitrogen content in the films increases, samples close to the
chromium target show hexagonal crystal structure with a large
crystallite size at Ar:N2 equal to 43:43, while for the samples
close to the aluminum target, the films do not have a well
defined crystal structure. Interestingly, there are some whiskers
observed on the films on oxidation in air. These whiskers were
more in concentration in the film at higher nitrogen flow rates as
can be seen from the Fig. 9(f ).
4. Conclusions
1. The composition of the Cr1−xAlxN films varied along the
length of the chamber axis from about 1.14 at.% of Al to
23 at.% of Al at all the deposition conditions.
2. The CrN x films exhibit highly columnar growth mode
when the substrate is oriented parallel to the flux of ion-
ized species. By contrast, the Cr1−xAl xN films exhibit
smoother morphology, with less pronounced columnar
habit, when the substrate is oriented normal to the flux of
ionized species.
3. The CrNx coatings got oxidized to α-Cr2O3 on heating in air
at 900 °C, while the Cr–Al–N films showed an improvement
in thermal stability.
4418 S.R. Pulugurtha, D.G. Bhat / Surface & Coatings Technology 201 (2006) 4411–4418
Acknowledgements
The authors acknowledge Alan Toland and Dr. John Shultz
of Arkansas Analytical Laboratory for their help with the
analysis, and Dr. Atul Khanna, post-doctoral research associate,
for his help during deposition experiments. The research was
funded by the National Science Foundation through Grant #
DMI-0400167.
References
[1] W. Kalss, A. Reiter, V. Derflinger, C. Gey, J.L. Endrino, 16th International
Plansee seminar, vol. 3, HM58, 2005, p. 136.
[2] R. Franz, B. Sartory, R. Kaindi, R. Tessadri, A. Reiter, V.H. Derflinger, P.
Polcik, C. Mitterer, 16th International Plansee seminar, vol. 3, HM58, 2005,
p. 930.
[3] O. Knotek, F. Loffler, H.J. Scholl, Surf. Coat. Technol. 45 (1991) 53.
[4] J. Vetter, E. Lugscheider, S.S. Guerreiro, Surf. Coat. Technol. 98 (1998) 1233.
[5] M. Kawate, A.K. Hashimoto, T. Suzuki, Surf. Coat. Technol. 165 (2003) 163.
[6] O. Banakh, P.E. Schmid, R. Sanjines, F. Levy, Surf. Coat. Technol. 163–164
(2003) 57.
[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.
Martinez-Martinez, C. Lopez-Cartes, A. Fernandez, Surf. Coat. Technol. 200
(2005) 192.
[9] J.C. Sanchez-Lopez, D. Martinez-Martinez, C. Lopez-Cartes, A. Fernan-
dez, M. Brizuela, A. Garcia-Luia, J.I. Onate, J. Vac. Sci. Technol., A, Vac.
Surf. Films 23 (4) (2005) 681.
[10] T. Kohara, H. Tamagaki, Y. Ikari, H. Fujiii, Surf. Coat. Technol. 185 (2004) 166.
[11] M. Astrand, T.I. Selinda, F. Fietzke, H. Klostermann, Surf. Coat. Technol.
188–189 (2004) 186.
[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.
[14] C. Liu, G. Bi, H. Ziegale, A. Leyland, A. Matthews, J. Vac. Sci. Technol.,
A, Vac. Surf. Films 20 (3) (2002) 772.
[15] A. Sugishima, H. Kajioka, Y. Makino, Surf. Coat. Technol. 97 (1997) 590.
[16] Y. Makino, K. Nogi, Surf. Coat. Technol. 98 (1998) 1008.
[17] M. Kawate, A. Kimura, T. Suzuki, J. Vac. Sci. Technol., A, Vac. Surf.
Films 20 (2) (2002) 569.
[18] H. Hasegawa, M. Kawate, T. Suzuki, Surf. Coat. Technol. 200 (2005) 2409.
[19] A. Reiter, V.H. Derflinger, B. Hanselmann, T. Bachmann, B. Sartory, Surf.
Coat. Technol. 200 (2005) 2114.