Effect of intrinsic stress on preferred orientation in AlN thin films

B. K. Gan, M. M. M. Bilek, D. R. McKenzie, M. B. Taylor, and D. G. McCulloch

Citation: Journal of Applied Physics 95, 2130 (2004); doi: 10.1063/1.1640462
View online: http://dx.doi.org/10.1063/1.1640462
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JOURNAL OF APPLIED PHYSICS

VOLUME 95, NUMBER 4

15 FEBRUARY 2004

Effect of intrinsic stress on preferred orientation in AlN thin films

B. K. Gan,a) M. M. M. Bilek, and D. R. McKenzie
Applied and Plasma Physics, School of Physics (A28), University of Sydney, New South Wales 2006,
Australia

M. B. Taylor and D. G. McCulloch

Department of Applied Physics, RMIT University, G.P.O. Box 2476V, Melbourne 3001, Australia

Received 27 August 2003; accepted 18 November 2003

We examine the effect of ion impact energy on the intrinsic stress and microstructure of aluminum
nitride thin films deposited using a filtered cathodic arc. The dependence of intrinsic stress on ion
impact energy is studied over the range from 0 to 350 V using dc bias and up to several kV for a
fraction of the ions using pulse bias. For dc bias, the stress reaches a maximum at 200 V and
decreases with further increase in ion bias. The preferred orientation of the crystallites was studied
by cross-section transmission electron microscopy and diffraction. We found that there is a
preference for the c crystallographic axis to lie in the plane of the film under high intrinsic stress
conditions 4 GPa, whereas a c-axis orientation perpendicular to the plane of the film was observed
for low intrinsic stress 0.25 GPa. We carried out calculations of the expected distribution of
intensity in cross-sectional electron diffraction patterns to predict the effect of rotation freedom of
crystallites with the c axis pinned. The calculated patterns agreed well with experiment. 2004
American Institute of Physics. DOI: 10.1063/1.1640462

I. INTRODUCTION

Many researchers have studied the evolution of intrinsic

residual stress in thin filmssee selected papers.110 The
degree of stress generated in these films is dependent on the
deposition conditions, such as the working pressure, substrate bias, etc.
A universal curve is observed for all materials relating
the intrinsic stress to the ion impact energy.11 The stress in
films deposited with low thermal energies 1 eV is usually
tensile. With increasing ion energy the stress becomes compressive, increasing to a maximum, and then decreasing.
Compressive stresses for materials as a function of the ion
energy used in synthesis have been reported. This behavior is
shown, for example, by chromium on silicon,4,5 titanium on
silicon,6 titanium nitride on tungsten carbide,7 and tetrahedral amorphous carbon on silicon.8
Aluminum nitride AlN is a IIIV semiconductor compound with a wide direct band gap and a high refractive
index. It is of interest for use in optoelectronic devices and as
a chemically inert barrier layer. AlN crystallizes in a hexagonal structure, and when grown as a thin film under conditions
that do not favor epitaxy, it forms as a granular microcrystalline material with the crystallite size determined by the
growth conditions. In the majority of cases the crystallites of
AlN thin films are found to have a preferred crystallographic
orientation with respect to the plane of the substrate.1219 In
most cases,1316 the preferred orientation reported is with the
c axis perpendicular to the plane of the film.
Windischmann,13 used a nitrogen ion bombardment energy
of 100 eV and reported intrinsic stresses of up to 2.8 GPa in
a

Author to whom correspondence should be addressed; electronic mail:

bkgan@physics.usyd.edu.au

AlN films with the c axis perpendicular to the film. For

growth using energies above 100 eV,1719 a change to a c
axis in the plane of the film orientation was reported for
energies between 300 and 500 eV.
In this article, we study the microstructure of films deposited using a filtered cathodic arc under the influence of
ion impact energies ranging from tens of electron volts to
several thousand electron volts. The changes in intrinsic
stress as a function of the ion energy are examined. A study
of the microstructure of the samples reveals a strong correlation between the stress and the preferred orientation, which
agrees with the model presented in Ref. 12.
II. EXPERIMENTAL DETAILS

All of the thin films reported in this article were deposited using a cathodic arc deposition system described
elsewhere.20 The cathode from which the Al plasma was ablated was a 50-mm-diam aluminum disk of purity 99%. The
arc current was 50 A and curved magnetic field coils were
used to steer the plasma to the substrate and eliminate macroparticles for the deposition of all films discussed here. The
films were deposited onto clean 310340-m-thick, 20
20 mm 100 Si wafers, polished on both sides.
Prior to deposition, the chamber was evacuated to a
vacuum base pressure of 2105 Torr. A background gas
with pressure 1.2103 Torr, consisting of a mixture of N2
and Ar gas, was admitted at flow rates of 7.0 and 2.0 sccm,
respectively. The arc was then initiated to produce an Al
plasma. The working pressure during deposition of AlN was
5104 Torr. These conditions were found to deposit stoichiometric AlN. To bias the substrate, a dc power supply
was employed. Samples were fabricated using dc bias ranging from 0 to 350 V, in steps of 50 V, with a deposition rate

0021-8979/2004/95(4)/2130/5/$22.00
2130
2004 American Institute of Physics
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J. Appl. Phys., Vol. 95, No. 4, 15 February 2004

FIG. 1. Residual stress in AlN vs bias energy, E and F are AlN films
prepared using earth and floating potentials, respectively.
1

of 3 nm min . Two lower stress samples were prepared by

high voltage pulsing: 8 kV, 800 Hz, and 2 kV, 600 Hz, with
pulse duration of 20 s. The deposition rate was 10
nm min1 and the substrate was earthed between high voltage pulses.
Stress was measured by observing the change in the radius of curvature of the Si substrate before and after deposition. The intrinsic stress f was calculated using Stoneys
equation:21

t s2 1 1
Es
f
,

6 1 s t f R R b
where E s is the Youngs modulus for the Si100 wafer 125
GPa, s is the Poissons ratio for the Si substrate 0.28, t s is
the thickness of the substrate, t f is the thickness of the film,
R is the radius of the curvature of the film on the substrate,
and R b is the radius of curvature of the bare substrate. Measurements of R and t f were carried on a surface profiler,
model Tencor P-10.
X-ray diffraction XRD was used to detect preferred
orientation in the AlN films. XRD data were collected using
Cu K 1.5418 radiation 40 kV, 40 mA, Bragg
Brentano 2 geometry with 2 mm divergence and 0.05
mm receiving slits, a graphite monochromator, 2
30 80, step size 0.02, and counting time of 10 s per
step. Peaks were identified using the JCPDSICDD x-ray
database, No. 25-1133 for aluminum nitride, hexagonal
structure.
Cross-sectional transmission electron microscopy
XTEM was carried out on selected samples. The XTEM
samples were thinned using a tripod polisher and diamond
paper followed by ion beam thinning. A combination of electron diffraction and dark field imaging was used to determine
the microstructure and any preferred orientation in the film.
The selected area diffraction patterns were taken using a circular aperture with a diameter of approximately 100 nm.
III. RESULTS AND DISCUSSION

Figure 1 shows the measured residual stress as a function of the bias on the substrate during deposition. The actual
ion impact energy will be somewhat higher than the applied
bias voltage for two reasons. First, the cathodic arc plasma
plume has a natural drift velocity normal to the cathode sur-

Gan et al.

2131

FIG. 2. XRD plot of a low stress AlN sample, deposited using 8 kV 20 s

pulses, 800 Hz. The film thickness is 230 nm and the film stress is 0.50 GPa.

face and the corresponding drift energy is added to the energy gained by the ions in falling through the potential from
the plasma to the substrate. This extra energy is of the order
of a few tens of electron volts. The second perturbation to the
impact energy arises from the fact that in an aluminum cathodic arc plasma there are some doubly, and even a few
triply, charged ions. Although their number is reduced due to
the presence of the background nitrogen gas, we expect that
a minority of ions will have higher charge states, and thus
will gain twice or three times the energy of a singly charged
ion when falling through the potential to the substrate.
It is clear from Fig. 1 that AlN shows a behavior similar
to most other materials, whereby residual stress initially increases with increasing energy and then begins to decrease.
Although our power supply could only maintain a maximum
dc voltage of 350 V we were able to access higher ion impact
energies by using a pulsed power supply, that could deliver
voltage pulses up to 20 kV for short periods of time. Application of such high voltage pulses of duration 20 s at frequencies of a few hundred Hz during the film growth reduced the residual stress to well below 1 GPa. The stress
reduction observed increased with increases in both the bias
voltage of the pulses and the frequency with which they are
applied. The lowest stress we achieved was 0.2 GPa using 7
kV pulses at 500 Hz. These results are described in detail
elsewhere.22
An XRD spectrum for a film deposited using pulses of 8
kV, 20 s duration, and with a repetition rate of 800 Hz, is
shown in Fig. 2. We prepared this film on two different substrates simultaneously. The film deposited on a thin Si wafer
was used to measure stress 0.50 GPa, while the film deposited on a glass slide was used to collect the XRD spectrum.
Figure 2 shows that the 0002 diffraction peak of AlN is the
only feature visible in the XRD spectrum. Its presence is
indicative of a preferred orientation of crystallites with the c
axis perpendicular to the plane of the film. We also observed
a monotonically decreasing background due to the amorphous glass substrate. The films with higher stress showed no
discernible features above the noise.
In order to determine the preferred orientation, if any, of
high stress samples, we prepared XTEM samples of films
grown with a dc bias of 0 V earth, 200 V, and 350 V.
We also prepared an XTEM sample of a pulsed bias film
with stress of 0.25 GPa, using 2 kV, 20 s pulses at 600 Hz.
The images and selected area diffraction patterns obtained

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Gan et al.

J. Appl. Phys., Vol. 95, No. 4, 15 February 2004

FIG. 4. a Cross-sectional view of a TEM sample deposited at a bias of

200 V. ML, mixing layer. b Selected area diffraction pattern of
a. c Predicted electron diffraction pattern for a cross-sectional sample
with texture corresponding to all crystallites with c axes in the film plane
horizontal in the diagram but unconstrained otherwise. d High resolution TEM image for the sample in a. Fringes labeled A have a spacing
0 , and fringes labeled B have a spacing of 2.4
of 2.7 101

101 1 .

FIG. 3. a Cross-sectional view of a TEM sample deposited at the earth

potential. CG, carbon glue and ML, mixing layer. b Selected area diffraction pattern of a.

from these samples are shown in Figs. 3 6. Figures 3a and

3b show a bright field transmission electron microscopy
TEM image of the 0 V bias sample and the selected area
diffraction pattern, respectively. The diffraction pattern in
Fig. 3b is correctly aligned with respect to the image in Fig.
3a. The cross-sectional image of the film shows the silicon
substrate right, amorphous carbon glue left, and the AlN
film, approximately 30 nm thick next to the carbon glue.
There is also a mixing layer, approximately 8 nm thick, between the film and the substrate caused by the initial sputter
cleaning in Ar of the silicon substrate using 3 kV, 20 s
pulses at 1200 Hz for approximately 10 min. The diffraction
pattern from the film can be indexed to the AlN crystal struc 0 , 0002, and 101
1
ture with rings corresponding to 101
reflections starting from the center of the diffraction pattern.
There is no clear preferred orientation in this case.
In the case of the 200 V bias film Figs. 4a and 4b,
the corresponding results show a broad arc corresponding to
0 -type reflections from AlN perpendicular to the film
101
surface and arcs parallel to the film surface corresponding to
0002 reflections from AlN. This type of diffraction pattern
strongly suggests preferred orientation within the film. In
order to interpret the electron diffraction patterns obtained
from the TEM cross sections we used a computer code written in Matlab and described elsewhere23 to calculate the

positions and intensities of the arcs expected to be observed

in XTEM samples with various c-axis orientations to the film
plane and otherwise free rotation around the c axis and film
normal. Reciprocal lattice contributions of allowed crystallite
orientations were summed, and those that intersected the
Ewald sphere were included in the calculated diffraction pattern. The intensities (IFF * ) were then modulated using
the equation
F hkl f Al 1e 2 i h/32k/3l/2
f N e 2 i h/32k/3 1/2u l e 2 i 1u l ,
where f Al and f N are the atomic scattering factors of Al and
N, respectively, and the parameter u has a value of 0.385.24
Figure 4c shows a calculated diffraction pattern for the case
of the c axis of the crystallites lying in the plane of the film
with free azimuthal rotation and free rotation about their c
axes. The plane of the film is located along the y direction,
and the x direction corresponds to the normal to the film and
substrate. The only rings that show arcs cutting the x axis
normal to the film plane are those corresponding to the
0 -, 112
0 -, and the 202
0 -type reflections. The
101
strongest reflection along the y axis i.e., in the film plane is
the c-axis reflection 0002. It appears as a bright spot, indicating that the c axis is constrained to lie in the film plane.
The preferred orientation observed in the XTEM analysis was compared by XRD. The c-axis in-plane orientation
places the 0002 planes in an orientation in which they are
not in the reflection condition for our 2 scan. Since the
0 , 112
0,
planes satisfying the reflection conditions 101

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Gan et al.

J. Appl. Phys., Vol. 95, No. 4, 15 February 2004

2133

FIG. 5. a Cross-sectional view of a TEM sample deposited at a bias of

350 V. ML, mixing layer. b Selected area diffraction pattern of a.

0 give only weak reflections, the XRD scan should

and 202
contain no resolvable peaks above the noise level.
In addition to the results shown in Figs. 4a and 4b,
we also collected a high resolution TEM image of the 200
V filmFig. 4d. It is clear from the lattice fringes observed
in this image that the AlN microstructure consists of an assemblage of crystal grains without evidence for any amorphous phase, even at the grain boundaries. This conclusion is
supported by the absence of any diffuse rings in the diffraction pattern of Fig. 4b.
Figure 5 shows the TEM results for the 350 V film. It
also reveals some evidence of preferred orientation similar to
that observed in the case of the 200 V film. The key difference, however, is the presence of many crystals with an
orientation with the c axis normal to the film. This indicates
that there are parts of the film which have reverted to the
same orientation as found in the film with no bias.
We also collected TEM images for a low stress film
0.25 GPa, prepared using pulses of 2 kV, 20 s duration
and with a repetition rate of 600 Hz. Figure 6 shows the
TEM image and selected area diffraction pattern for this
sample. The strong 0002 refractions along the axis perpendicular to the plane of the film in Fig. 6b show that the
crystallites in this sample are preferentially aligned with the
0002 direction normal to the plane of the film. The predicted diffraction pattern in Fig. 6c for such crystallites also
supports this result.

FIG. 6. a Cross-sectional view of a TEM sample deposited using 2 kV 20

s pulses, 600 Hz. Film stress is 0.25 GPa. ML, mixing layer. b Selected
area diffraction pattern of a, clearly showing the 0002 orientation. c
Predicted electron diffraction pattern for a cross-sectional sample with texture corresponding to all crystallites with the c axis perpendicular to the film
plane.

IV. CONCLUSIONS

Our results show that AlN deposited by cathodic arc in a

background nitrogen atmosphere shows increasing residual
stress with increasing incident ion energy up to a maximum
at an applied bias of around 200 V. As the impact energy
on the growth surface is increased further, the residual stress
in the film starts to decrease. Pulsed biasing using very high
energies of several kV can be used to significantly relieve the
stress.
We observe a strong correlation between the residual
stress and the preferred orientation of the AlN film. In all of
the cases where the stress was lower than 1 GPa, the favored
orientation has the c axis of the crystallites positioned normal

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2134

to the plane of the film. When the stress is high, such as

3.5 4 GPa, the diffraction pattern obtained in XTEM is consistent with that predicted for a situation where the c axis of
the crystals is constrained to lie in the plane of the film, but
free as to its orientation in that plane and its rotation about
the crystallite c axes. This change from c in plane to c orthogonal to the film plane is consistent with the prediction of
the thermodynamic theory.12 In this model the preferred orientations arise from the need to minimize the free energy of
the system, which includes the strain energy associated with
the residual compressive stress. It is thus expected that at
high stresses the orientations with the lowest contributions to
the total strain energy should dominate, while at low values
of stress surface and interface contributions will dominate.
The model presented in Ref. 12 predicted that the c axis in
the plane of the film should be the one with the lowest strain
energy contribution, and thus should appear in high stress
films. The calculation was based on elastic constants published by McNeil et al.25 The fact that the predictions of the
model were noted to be very sensitive to changes in elastic
constants is noted, and further work on the possible values of
these constants in films deposited under various conditions is
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