Thin Solid Films 406 (2002) 159–163

Effects of nitrogen flow rates on the growth morphology of TiAlN films

prepared by an rf-reactive sputtering technique
K. Chakrabarti, J.J. Jeong, S.K. Hwang, Y.C. Yoo, C.M. Lee*
School of Materials Science and Engineering, Inha University, 253 Youngheyon-dong, Inchon 402-751, South Korea

Received 24 January 2001; received in revised form 11 July 2001; accepted 7 December 2001

Abstract

Over the last decade titanium aluminum nitride (TiAlN) has been under active investigation as a promising alternative to binary
coating materials for cutting and forming tools because of its superior oxidation resistance and lower thermal conductivity.
However, the effects of nitrogen flow rates on the reactive sputtering of TiAlN films remain relatively untapped despite their
importance in studying the growth morphology to acquire valuable knowledge for the selection of optimum coating conditions.
In this paper we report the results of our study regarding the implications of nitrogen flow rate on the growth morphology of the
TiAlN films reactively sputtered from a stoichiometric target of TiAl. Scanning and transmission microscopy (SEM, TEM), X-
ray diffraction (XRD) and atomic force microscopy (AFM) have been used for film characterization, the latter of which is yet
to be fully exploited as a tool for analyzing the effects of N2 as a sputtering parameter. 䊚 2002 Elsevier Science B.V. All rights
reserved.

Keywords: TiAlN; Sputtering; Structural properties; Atomic force microscopy

1. Introduction TiAlN coatings are mostly synthesized through reactive

Titanium aluminum nitride (TiAlN) has been devel-
oped and has been under active investigation since last
decade as a promising alternative to binary coating
materials for cutting and forming tools w1–5x. Very
recently titanium aluminum nitride coatings have also
been studied for applications other than in tribology;
e.g. in satellite temperature control w5x. A fundamental
advantage of TiAlN coatings is that they form a highly
adhesive, dense protective Al2O3 film at their surface
when heated, preventing further inward diffusion of
oxygen into the coated material w6x. In addition, they
have lower thermal conductivity, making them particu-
larly suitable as coatings for machining applications.
The superior cutting behavior of TiAlN over conven-
tional binary coatings makes it a suitable candidate for
high-speed cutting tools.
Although there are a few reports of TiAlN deposition
by chemical vapor deposition (CVD) techniques w7,8x,
*Corresponding author. Tel.: q82-32-860-7536; fax: q82-32-862-
5546.
E-mail address: cmlee@inha.ac.kr (C.M. Lee).
physical vapor deposition (PVD) methods such as sput-
tering w9,10x or ion plating w11x. In recent years, we
have seen reports on several aspects of TiAlN sputter
deposited films, but those describing the effects of
nitrogen flow rates on the reactive sputtering of TiAlN
films w10x remain quite scarce. In particular, atomic
force microscopy (AFM), which is an important probe
not only to study the top surface morphology of the
films, but also to obtain information on the average
grain size, the roughness, the size and shape distribution
of the islands, remain an untouched tool in analyzing
the effects of the nitrogen flow rate as a sputtering
parameter.
The purpose of this work is to study the implications
of nitrogen flow rate on the reactive sputtering of TiAlN
films from a stoichiometric target of TiAl by scanning
and transmission electron microscopy (SEM, TEM), X-
ray diffraction (XRD) and AFM.
2. Experimental details
TiAlN films with a thickness of ;0.4–0.5 mm were
deposited on Si(100) substrates by rf-sputtering from a

0040-6090/02/$ - see front matter 䊚 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 4 0 - 6 0 9 0 Ž 0 1 . 0 1 7 9 1 - 6
160 K. Chakrabarti et al. / Thin Solid Films 406 (2002) 159–163
Table 1
Deposition conditions
Base pressure 7=10y7 mbar
Deposition pressure 4=10y3 mbar
Substrate temperature 300 8C
Substrate rotation 3 rev.ymin
rf-Power 450 Watts
N2 flow rate 10–25 sccm
Ar flow rate 25 sccm
Deposition time 75 min
stoichiometric TiAl target under various N2 and Ar flow
rates in a stainless steel chamber. In our study we kept
the Ar flow rate fixed at 25 sccm and N2 flow was
varied in the range of 10–25 sccm. The pumping speed
was also adjusted to keep the N2 partial pressure
constant. Prior to the introduction into the chamber the
Si substrates were ultrasonically cleaned in a solution
consisting of HF, HNO3 and H2O (1:1:5). A turbomo-
lecular pump was used to achieve a base pressure of
7=10y7 mbar before introducing the gas mixtures. The
details of the deposition conditions are given in Table
1.
The texture and phases of the prepared films were
characterized by X-ray diffraction using CuKa radiation
by a Philips PW 3719 X-ray diffractometer. SEM and
energy dispersive X-ray (EDX) analysis were performed
using a Hitachi S-4200 Scanning electron microscope &
Kevex systems. To prepare cross-sectional TEM speci-
mens, small pieces of the sample were cemented film
to film by epoxy resin. They were then mechanically
ground to a thickness up to 90 mm and thereafter dimple
grinding was performed up to 10 mm. Finally argon ion
milling was conducted. A 200 kV (model: Philips
CM200) transmission electron microscope was used to
examine the samples. AFM analyses were performed
with scanning probe microscopy (Topometrix Corpora-
tion: Accurex II) at room temperature.
3. Results and discussion
3.1. XRD analysis
Fig. 1 shows the XRD patterns of different TiAlN
films prepared under different N2 flow rate conditions.
It is quite clear from the above figure that the XRD
spectra for all films exhibited relatively intense (200)
peak of the NaCl structure of TiN. TiAlN films of a
strong preferred orientation of (200) were also reported
by others w12,13x. According to the report of Shew et
al. w10x the high flow rate of N2 (above 6 sccm) reduces
the (111) peak intensity, while it increases the (200)
peak intensity. This is due to the fact that the (111)
plane, having the lowest surface energy in a fcc TiAlN
structure, provides the favorable sites of stacking for the
mobile atoms, resulting in the lowest energy crystal
facets parallel to the substrate under relatively intense
bombardment w10x. With the increasing nitrogen flow
rate, the nitrogen atomyion flux increases and the
mobility of the adatoms decreases. This could favor the
growth of crystal planes having higher surface energy,
i.e. (200), at the expense of others because of its higher
ledge density and the shorter diffusion distance to the
relatively lower energy sites w14x.
From EDX analysis it was found that our TiAlN films
can best be expressed as Ti1yxAlxN, with xs0.51–0.57
with decreasing N2 flow rate. It was shown w15,16x that
the sputtered Ti1yxAlxN films consist of two phases;
one with the B1-NaCl structure AlN depleted Ti1yxAlxN
(002) grains, and another wurtzite-structure of AlN-rich
(0002) and (1011) ¯ grains for 0.52-xF0.59. In the
XRD patterns of Fig. 1, the peaks decrease in intensity
and broaden as an additional broad peak corresponding
¯ plane diffraction of the wurtzite-structure
to the (1011)
overlaps at the same 2u position w13x. It may be noted
here that a similar phenomenon was reported by us w17x
very recently for Ti1yxYxN systems, although the rela-
tive effect of Y was found to be stronger than Al.
3.2. Electron microscopy
Fig. 2 shows the surface and cross-sectional scanning
electron micrographs of two films deposited at different
nitrogen flow rates. It is evident that the TiAlN films
have a columnar structure with voids and boundaries
throughout the film thickness (Fig. 2a,c). This growth
process is similar to that reported for TiN w18,19x. The
surface morphology is similar for both cases excepting
that the films formed under a higher nitrogen flow rate
has less clustering of grains (Fig. 2d). It is also evident
from Fig. 2 that the film deposited at the N2 flow rate
of 25 sccm (Fig. 2c) has a much denser and finer
grained morphology compared with that deposited at the
N2 flow rate of 10 sccm (Fig. 2a). This morphological
Fig. 1. XRD patterns of different TiAlN films deposited with N2 flow
rates of 20 sccm (a), 15 sccm (b), 12 sccm (c), 10 sccm (d) and 8
sccm (e), keeping the Ar flow rate fixed at 25 sccm. Panel (f) is the
reference TiN pattern sputter deposited with Ti target with N2 and Ar
flow rates being 10 sccm and 25 sccm, respectively.
 K. Chakrabarti et al. / Thin Solid Films 406 (2002) 159–163 161

Fig. 2. Cross-sectional scanning electron micrographs of two films

deposited with N2 flow rates of 10 sccm (a) and 25 sccm (c). (b)
and (d) show the surface morphologies of (a) and (c), respectively.

difference is very important for the oxidation of the

films since oxygen can diffuse through the column and
grain boundaries. Hones et al. w19x have shown that in
the case of the binary TiN system the morphology of
the coatings significantly influences the oxidation rate
and films with a pronounced columnar morphology
oxidize more than seven times faster than those with a
dense and fine-grained morphology. Thus, for TiAlN
films deposited at higher N2 flow rates (and consequent-
ly of denser morphology) are expected to show better
oxidation resistance. Fig. 4. AFM images of films deposited with N2 flow rates of (a) 10
Fig. 3 shows the cross-sectional transmission electron sccm and (b) 20 sccm.
micrographs and corresponding selected area diffraction
pattern (SADP) for two films deposited at the nitrogen flow rates of 10 sccm (Fig. 3a,b) and 20 sccm (Fig.
3c,d), respectively. Cross-sectional SEM micrographs
also confirm the columnar growth. The average crystal-
lite size was estimated from enlarged SEM micrographs,
as well as from the X-ray line broadening using Sherrer’s

Fig. 3. Cross-sectional transmission electron micrographs of two films

deposited with N2 flow rates of (a) 10 sccm and (c) 20 sccm. (b)
and (d) show the corresponding selected area diffraction patterns for Fig. 5. Variation of surface roughness with N2 flow rate, with Ar flow
(a) and (c), respectively. rate fixed at 25 sccm.
162 K. Chakrabarti et al. / Thin Solid Films 406 (2002) 159–163
˚ and bearing ratio win percent (%)x for films with N2 flow rates of (a) 10 sccm, (b)
Fig. 6. Line profiles showing the height distribution (in A)
12 sccm, (c) 15 sccm and (d) 20 sccm. Ar flow rate was kept constant at 25 sccm. The maximum depth probed by the AFM tip was taken as
height zero.
equation given by:
Ds0.9ly Žbcosu.
where D is the average particle size, l is the X-ray
wavelength, b is the diffraction line broadening (in
radians) and u is the diffraction angle. The average
crystallite size was found to be ;5–10 nm, with a
discrepancy of less than 3% between the values obtained
by two methods. The rings of the diffraction patterns
are characteristic of a single crystal phase in a polycrys-
talline state. This observation is in good agreement with
that observed by Ikeda et al. w7x. It may also be noted
that a few very weak intensity rings indicative of the
presence of very minor phases, have also been detected
from the diffraction patterns.
3.3. AFM analysis
AFM images were obtained using a 100 mm scanner
to investigate the top surface morphology of the films.
The thickness and the RMS roughness of the film were
estimated from the average of several scans. Two
zoomed images of 3 mm=3 mm area of TiAlN films
deposited at the N2 flow rates of 10 sccm and 20 sccm
are shown in Fig. 4. It can be seen that the film surfaces
are fairly smooth with an average RMS roughness of
;2.3 nm and 1.8 nm, respectively. It may be noted here
(1)
that the roughness, mentioned above, is the convolution
of the shape and local roughness. This RMS roughness
is mostly dominated by the shape of overlapping islands,
of which the films are composed, and not by the local
roughness of the individual islands, which was found to
be several orders smaller compared with the roughness
mentioned above. Fig. 5 shows a plot of surface rough-
ness vs. N2 flow rate. The decrease in roughness with
the increase in N2 flow rate may be attributed to the
fact that the films prepared at a higher N2 flow rate
gives a denser and finer morphology compared with
that prepared with a lower N2 flow rate, as is evident
from the SEM micrographs.
We have also studied the line profile of the height
distribution and the bearing ratio (which is a measure
of the relative size of the bearing surface, where the
bearing surface is the maximum surface area which is
exposed above a certain z-plane) as can be seen from
Fig. 6. Fluctuations around the mean surface observed
in the line profiles are indicative of defects of different
sizes and heights arising out of grain domains without
well-defined size. However, the bearing ratio goes to
 K. Chakrabarti et al. / Thin Solid Films 406 (2002) 159–163
zero value beyond 11.4 nm and 14.5 nm, respectively,
for films deposited at the N2 flow rate of 10 and 20
sccm. This indicates that within the resolution governed
by the scan size and the aspect ratio of the tip of the
indenter, islands are connected to each other at this
depth from the surface. The average shape of the islands
as a function of depth can also be found from the
bearing ratio as pointed out by Kundu et al. w20x.
4. Conclusions
From the present study on TiAlN films deposited on
Si(100) by rf-sputtering, the following conclusions may
be drawn:
1. The films deposited using this technique are prefera-
bly (200) oriented of NaCl structure of TiN. However,
for lower nitrogen flow rates the (200) diffraction
peak decreases in intensity and broadens as an addi-
¯ wurtzite-structure alloys over-
tional peak of (1011)
laps at the same 2u value.
2. From SEM and TEM analysis it was found that the
film growth takes place with a columnar morphology.
With an increase in N2 flow rate the columns become
denser. TEM selected area diffractograms show the
presence of a dominant single crystal phase in a
polycrystalline state.
3. AFM indicates a fluctuating surface morphology
mainly arising out of the grain domains distribution
in a random fashion. The surface roughness was
found to tend to a constant value at higher nitrogen
flow rates. The bearing ratio has also been plotted as
a function of height, taking the maximum depth
probed by the AFM tip as zero height.
The above study is expected to help determine the
optimum coating conditions for making dense and
smooth TiAlN films by the reactive sputtering technique
in the future.
163
Acknowledgments
This work was financially supported by the Korea
Research Foundation through the BK21program.
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